# NiMH: Wikis

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Energy/weight Modern, high capacity NiMH rechargeable cells 30–80 W·h/kg 140–300 W·h/L 250–1000 W/kg 66%[1] 2.75 W·h/US\$[1] 30%/month (temperature dependent)[2] Citation Needed 500–1,000 1.2 V

A nickel-metal hydride cell, abbreviated NiMH, is a type of secondary electrochemical cell similar to the nickel-cadmium cell. The NiMH battery uses a hydrogen-absorbing alloy for the negative electrode instead of cadmium. As in NiCd cells, the positive electrode is nickel oxyhydroxide (NiOOH). An NiMH battery can have two to three times the capacity of an equivalent size nickel-cadmium battery. However, compared to the lithium-ion cell, the volumetric energy density is lower and self-discharge is higher. (Compare: low self-discharge NiMH battery)

Common AA cells (penlight-size) NiMH batteries have nominal charge capacities (C) ranging from 1100 mA·h to 2900 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).

## History

The first consumer grade NiMH cells for smaller applications appeared on the market in 1989 as a variation of the 1970s' Nickel hydrogen battery[3]. Positive electrode development was done by Dr. Masahiko Oshitani from GS Yuasa Company, who was the first to develop high-energy paste electrode technology. The association of this high-energy electrode with high-energy hybrid 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 cell.

## Battelle-Geneva's pioneering work on NiMH, 1967

The pioneering work on NiMH batteries – essentially based on sintered Ti2Ni+TiNi+x alloys for the negative electrode and NiOOH-electrodes for the positives – was performed at the Battelle Geneva Research Center starting after its invention in 1967: The development work was sponsored over nearly 2 decades by Daimler-Benz Comp./Stuttgart and by Volkswagen AG. within the framework of Deutsche Automobilgesellschaft. The batteries showed high energy density up to 50 W·h/kg (180 kJ/kg), power density up to 1000 W/kg and a reasonable deep cycle life of 500 cycles (DOD=100%). Patent applications were filed in European countries (priority: Switzerland) , USA and Japan and the patents transferred to Daimler-Benz Comp./Stuttgart. Ref: Elektrode zur Speicherung und Aktivierung von Wasserstoff", Inventor: K.D. Beccu, Battelle-Geneva, Swiss Priority Application No. 6333/67-Bb3/CH/2 - (2.05.1967), Patent: DE 2317505 C2 (18.10.73). Negative electrode of Ti-Ni alloy hydride phases, US patent US 3,669,745 (06/13,1972), inventor: K.D. Beccu, Ph.D, Battelle-Geneva R&D Center. See also "History and other Information" in the Discussion Section.

The NiMH cells developed by Philips Laboratories and French CNRS (see above) were based on rare earth metal alloys. They suffered from the instability of the alloys in alkaline electrolyte and consequently insufficient cycle life.

Ovonic Battery Comp. in Michigan, USA altered and improved the Ti-Ni alloy structure and composition according to their patent and licensed NiMH batteries to over 50 companies worldwide. The "invented NiMH variation" of Ovonics consisted in special alloys with disordered alloy structure and specific multicomponent alloy compositions. Unfortunately linked to their composition, calendar and cycle life of such alloys always remain very low, and all NiMH batteries manufactured at present time in the world consist in AB5 type rare earth metal alloys. Currently, more than 2 million hybrid cars worldwide are running with NiMH batteries,{ref: Avicenne Conf., Nice 2008, M.A. Fetcenko/ECD} e.g. Prius, Lexus (Toyota), Civic, Insight (Honda), Fusion (Ford) and others. A large proportion of these batteries is manufactured by PEVE (Panasonic) and Sanyo.

## Applications

High power Ni-MH Battery of Toyota NHW20 Prius, Japan
Nickel-metal hydride battery made by Varta, Museum Autovision, Altlussheim, Germany

Applications of NiMH electric vehicle batteries includes all-electric plug-in vehicles such as the General Motors EV1, Honda EV Plus, Ford Ranger EV and Vectrix scooter. Hybrid vehicles such as the Toyota Prius, Honda Insight, Ford Escape Hybrid, Chevrolet Malibu Hybrid, and Honda Civic Hybrid also use them. NiMH technology is used extensively in rechargeable batteries for consumer electronics, and it 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.

## Electrochemistry

The negative electrode reaction occurring in a NiMH cell is

$\mathrm{H_2O + M + e^- \leftrightharpoons OH^- + MH}.$

The charge reaction is read left-to-right and the discharge reaction is read right-to-left.

On the positive electrode, nickel oxyhydroxide (NiOOH) is formed,

$\mathrm{Ni(OH)_2 + OH^- \leftrightharpoons NiO(OH) + H_2O + e^-.}$

The "metal" M in the negative electrode of a NiMH cell 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 aluminium. Very few cells 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[4]. 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 cells to remain sealed in normal operation and to be maintenance-free.

NiMH cells have an alkaline electrolyte, usually potassium hydroxide. For separation hydrophilic polyolefin nonwovens are used.[5]

## Charging

NiMH Charge curve

The charging voltage is in the range of 1.4–1.6 V/cell. A fully-charged cell measures 1.4–1.45 V (unloaded), and supplies a nominal average 1.25 V/cell during discharge, down to about 1.0–1.1 V/cell (further discharge may cause permanent damage). This voltage varies depending on the discharge rate of the cell (lower discharge loads result in an increased voltage output for longer periods, approaching the 1.4 V unloaded cell voltage). In general, a constant-voltage charging method cannot be used for automatic charging. When fast-charging, it is advisable to charge the NiMH cells with a smart battery charger to avoid overcharging, which can damage cells and cause dangerous conditions. A NiCd charger should not be used as an automatic substitute for a NiMH charger.[6]

### ΔV charging method

According to Panasonic and other NiMH cell manufacturers, the ΔV" method is one of the preferred charging methods for charging. The charger measures the rate of change (signified by the symbol Δ) of the voltage of the cell (signified by the letter V). This is illustrated in the "NiMH charge curve" figure. The cell or battery is rapidly charged at a constant current of 1 C/h, where C is the capacity of the battery (the capacity is expressed in ampere hours, or more commonly milliampere hours (mA·h). After the cell is fully charged, and as it begins to overcharge, the voltage polarity of the electrodes inside the battery will begin to reverse, and this will cause the battery voltage to decrease slightly. A ΔV type battery charger ends the charge cycle by switching off the charging current when it senses this drop in voltage. In some cases, a very small "trickle charge" may remain. The "charge curve" graph also shows that the charge voltage will change depending on the charge current (it also changes with temperature and battery age). This generally means that a constant-voltage charging method cannot be used automatically, because it will either be unsafe, or it will not charge batteries reliably and consistently. This is unlike a lead-acid cell for example, which can, in theory, be more easily charged at a suitably chosen constant voltage.[6]

### ΔT temperature charging method

The ΔT temperature change method is similar in principle to the ΔV method. Because the charging voltage is nearly constant, if constant-current charging is used, then a near constant power is entering the cell. When the cell is charging, most of this power will be converted to chemical energy. However, when the cell is fully charged, most of the charging power will then be converted to heat. This results in an increase in the rate of change of temperature, which can be detected by a sensor measuring the battery temperature.

### Manual charging

If a suitable battery charger is not available, constant-voltage or constant-current charging can be done manually, at a moderately high charging rate, if careful attention is given. For proper charging, the voltage and/or current must be set to a suitable charging rate for the particular battery, and a timer should be set. Periodic monitoring is strongly recommended to avoid overcharging (resulting in a voltage drop), or overheating (resulting in an excessive temperature rise and possibly an overpressure condition).[citation needed]

It is safer just to use a C/5 or C/10 charge-rate. [7]

### Trickle charging

Some equipment manufacturers consider that NiMH cells can be safely charged in simple fixed, low-current chargers with or without timers, and that permanent overcharging is permissible with currents up to 0.1 C/h. According to the Panasonic NiMH charging manual, extensive trickle charging can cause battery deterioration due to overcharging, and it is the least preferred charging method concerning battery performance. If it is used, the trickle charge rate should be limited to between 0.033 C/h and 0.05 C/h for a maximum of 20 hours to avoid damaging the batteries.[6]

For a slow charge, or "trickle charge" process, Duracell recommends "a maintenance charge of indefinite duration at 0.0033 C/h".[8] Some chargers do this after the charge cycle, to offset the natural self-discharge rate of the battery. To maximize battery life, the preferred charge method of NiMH cells uses low duty cycle pulses of high current rather than continuous low current.

### Safety

A good safety feature of a custom-built charger is to use a resettable fuse in series with the cell, particularly of the bimetallic strip type. This fuse will open if either the current or the temperature goes too high.[6]

Modern NiMH cells 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 0.1C (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.[6] 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.

There is an inherent risk with NiMH chemistry that overcharging will cause a buildup of hydrogen, causing the cell to rupture. Therefore, cells have a vent. Hydrogen will be emitted from the vent in the event of serious overcharging.[9]

### Loss of capacity

Voltage depression ("memory effect") from repeated partial discharge can occur, but is reversible through charge cycling.[10]

### Patent encumbrance

NiMH batteries suitable for use in electric vehicles and plug-in hybrids are tightly patented and have not been licensed for use by manufacturers, thereby slowing the development of new models.[11][12][13][14]

## Discharging

Under a light load (0.5 ampere), the starting voltage of a freshly charged AA NiMH cell in good condition is about 1.4 volts; some measure almost 1.5 volts. This voltage falls rapidly to about 1.25 volts at 10% depth of discharge (DOD) and then remains almost constant until the cell is over 80% discharged. The voltage then falls rapidly from about 1.2 volts down to 0.8–1.0 volts at which the cell is considered "flat" in most devices. Mid-discharge at a load of 1 ampere, the output is about 1.2 volts; at 2 amperes, about 1.15 volts; the total effective differential internal resistance is about 0.05 ohms. Nickel metal hydride batteries provide a relatively constant voltage for most of the discharge cycle, unlike a standard alkaline where the voltage falls steadily during discharge. [15]

### Over-discharging

A complete discharge of a cell until it goes into polarity reversal can cause permanent damage to the cell. This situation can occur in the common arrangement of four AA cells in series in a digital camera, where one will be completely discharged before the others due to small differences in capacity among the cells. 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 auto-shutdown, but devices like flashlights and some toys do not. 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.

Irreversible damage from polarity reversal is a particular danger in systems, even when a low voltage threshold cutout is employed, where cells in the battery are of different temperatures. This is because the capacity of NiMH cells significantly declines as the cells are cooled. This results in a lower voltage under load of the colder cells.[16]

### Self-discharge

NiMH cells historically had a somewhat higher self-discharge rate (equivalent to internal leakage) than NiCd cells. The self-discharge is 5–10% on the first day and stabilizes around 0.5–1% per day at room temperature.[17][18][19][20][21] 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 (>8000 mA·h) are reported to have the highest self-discharge rates.

### Low self-discharge cells

A new type of nickel-metal hydride cell was introduced in 2005 that reduces self-discharge and therefore lengthens shelf life. By using a new separator, manufacturers claim the cells retain 70–85% of their capacity after one year when stored at 20 °C (68 °F). These cells are marketed as "hybrid", "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.

Low self-discharge cells have lower capacity than some standard NiMH cells due to the larger area of the separator. The highest capacity low-self-discharge cells have 2000–2450 mA·h and 850 mA·h capacities for AA and AAA cells respectively, compared to 2800 mA·h and 1000 mA·h for standard AA and AAA cells. But C types are typically higher than their usual NiMH cousins with 4000 mA·h and the D type being 8000 mA·h.

However, after only a few weeks of storage, the retained capacity of low-self-discharge batteries often exceeds that of traditional NiMH batteries of higher capacity.[22]

## Environmental impact

Improper disposal of NiMH batteries poses less environmental hazard than that of NiCd because of the absence of toxic cadmium. However, mining and processing the various alternate metals that form the negative electrode may be expected to pose other types of environmental impact, depending on the metal, mining method, and environmental practices of the mine.

Most industrial nickel is recycled, due to the relatively easy retrieval of the metal from scrap, and due to its high value.

## Comparison with other battery types

NiMH cells 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 cells are somewhat available, but are often just a AA core hidden in an outer shell, with a rating of about 2500 mA·h, much less than ordinary alkaline C and D batteries.[citation needed] Real NiMH C and D batteries are expensive (and the chargers are uncommon); they should be rated at least 5000 mA·h for C and 10,000 mA·h for D sizes.[23]

PP3 (nine volt) NiMH batteries are available; these usually have an output voltage of 8.4 V (1.2 × 7) and a capacity of roughly 200 mA·h.[citation needed] Also available are eight-cell nine volt batteries with a nominal output voltage of 9.6 V (1.2 × 8).

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

NiMH cells are often used in digital cameras and other high drain devices, where they often vastly outperform primary batteries even on a single charge. 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 cells.[24]

NiMH cells 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 about 700 mA·h capacity with a 1000 mA load.[25] Digital cameras with LCDs and flashlights can draw over 1000 mA, quickly depleting alkaline batteries. NiMH cells can deliver these current levels and maintain their full capacity.

Certain devices that were designed to operate using primary alkaline chemistry (or zinc-carbon/chloride) cells will not function when one uses NiMH cells as substitutes. However, this is rare, as most devices compensate for the voltage drop of an alkaline as it discharges down to about 1 volt. A good-quality freshly charged NiMH cell delivers 1.4–1.45 V, very close to the 1.5 V that these devices expect. Such devices would also likely have an extremely short runtime as the voltage from an alkaline falls to 1.4 V quite quickly from the 1.5 V starting voltage. Low internal resistance allows NiMH cells to deliver a near-constant voltage until they are almost completely discharged. This will result in a battery level indicator to overstate the remaining charge if it was designed to read only the voltage curve of alkaline cells. The voltage of alkaline cells decreases steadily during most of the discharge cycle.

Lithium ion batteries have a higher energy density than nickel-metal hydride batteries.[26] But they also have a much lower shelf-life and are significantly more expensive to produce.[27] In October 2009, ECD Ovonics announced that their next-generation NiMH batteries will provide specific energy and power that are comparable to those of lithium ion batteries at a cost that is significantly lower than the cost of lithium ion batteries.[28]

## References

1. ^ a b NiMH Battery Charging Basics "NiMH Battery Charging Basics". http://www.powerstream.com/NiMH.htm NiMH Battery Charging Basics.
2. ^ "What's the Best Battery?". Battery University. November 2006. Retrieved August 2007.
3. ^ In search of the perfect battery
4. ^
5. ^ Japanese Nonwoven Battery Applications
6. ^ a b c d e Panasonic's recommended NiMH charging methods, technical info (see the PDF's at this link)
7. ^ http://wiki.laptop.org/go/Battery_Charging#NiMH_Batteries
8. ^ Duracell NiMH charging methods
9. ^ Mukund R. Patel (2005), "Spacecraft Power Systems" CRC Press ISBN 9780849327865 Page 209
10. ^ "Voltage Depression ("Memory Effect")". Duracell.com. Retrieved July 2007.
11. ^ Sherry Boschert (2006). Plug-in Hybrids: The Cars that will Recharge America. New Society Publishers, Gabriola Island, Canada. ISBN 978-0-86571-571-4.
12. ^ Shnayerson, Michael (1996-08-27). The Car That Could: The Inside Story of GM’s Revolutionary Electric Vehicle. Random House. pp. 194-207, 263-264. ISBN: 978-0679421054.
13. ^ Coker, M. (2003-05-15). "Dude, Wheres My Electric Car!?!". Orange County Weekly. Retrieved 2009-10-08.
14. ^ Greenberg J. (2008-10-14). "The Edison of our Age: Stan Ovshinsky and the Future of Energy (Video Interview Part 1)". The Energy Roadmap. Retrieved 2009-10-08.
15. ^ NiMh Battery Shoot Out SilverFox, 2005–2008
16. ^ Sandeep Dhameja (2002), Electric Vehicle Battery Systems, Newnes, ISBN 0750699167, pp. 118, 123
17. ^ "Nickel-Metal Hydride (NiMH) Battery Charger and Battery Pack. User’s Manual.". Sea-Bird Electronics, Inc.. Retrieved 2009-07-10. "NiMH batteries self-discharge up to 20% in the first 24 hours after charging, then as much as 15% per month. Self-discharge is highly temperature dependent. NiMH batteries self discharge about three times faster at 40 °C than at 20 °C. Age also effects self-discharge. Older battery packs self-discharge faster than new ones."
18. ^ "epanorama.net: Battery Power Supply Page". Retrieved 2009-07-10. "A NiMH battery can lose up to 2% of its charge per day sitting on the shelf."
19. ^ "Battery Nurse: VCS, Voltage Control System". Retrieved 2009-07-10. "NiMh batteries tend to self-discharge at 3–4% of capacity per day."
20. ^ "Choosing the Right Battery Pack". Retrieved 2009-07-10. "Nickel Metal Hydride (NiMh) Approx 1% per day if unused."
21. ^ gpbatteries.com "GP Batteries (Hong Kong) FAQ". http://www.gpbatteries.com/html/faq/index.html gpbatteries.com. Retrieved 2009-07-10. "18. What is the self-discharge rate of NiMH batteries? In general, the rate of self-discharge ranges from 15% to 20% per month at room temperature."
22. ^ stefanv.com: Review: Testing Sanyo's Eneloop Rechargeable Battery
23. ^ Product information for Powerex rechargeable D cells
24. ^ Choosing and Using NiMH Rechargeable Batteries
25. ^ Alkaline Drain Chart at greenbatteries.com
26. ^ "Mitsubishi Heavy to make lithium ion car batteries". Yahoo finance, Singapore, quoting Reuters. 23 January 2007. Retrieved July 2007.
27. ^ http://www.ovonics.com/PDFs/Batteries2009OctoberNiceConference.pdf
28. ^ http://www.ovonics.com/PDFs/Batteries2009OctoberNiceConference.pdf