NICKEL-METAL HYDRIDE BATTERY
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(Redirected from NiMH)
A 'nickel-metal hydride battery', abbreviated 'NiMH', is a type of rechargeable battery similar to a nickel-cadmium (NiCd) battery but has a hydrogen-absorbing alloy for the anode instead of cadmium. Like in NiCd batteries, nickel is the cathode. A NiMH battery can have two to three times the capacity of an equivalent size NiCd and the memory effect is not as significant. 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 capacities ''C'' ranging from 1100 mA·h to 2700 mA·h at 1.2 V, usually rated at 0.2×''C'' rate. Useful discharge capacity is an inverse function of the discharge rate, but up to around 1×''C'' rate, there is no significant difference.
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).
NiMH battery technology was developed at the end of the 1980s and commercialised first by the Matsushita Company .
Applications of NiMH type batteries includes 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 and RC cars.
The anode reaction occurring in a NiMH battery is as follows:
H2O + M + e− ↔ OH− + M-H
The battery is charged in the right direction of this equation and discharged in the left direction.
Nickel(II) hydroxide forms the cathode.
The "metal" in the anode 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 hydrogen ions are forced out of the potassium hydroxide electrolyte solution by the voltage applied during charging, this process prevents them from forming a gas, allowing a low pressure and volume to be maintained. As the battery is discharged, these same ions are released to participate in the reverse reaction.
NiMH batteries have an alkaline electrolyte, usually potassium hydroxide.
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 1.2V during discharge, down to about 1.0V (further discharge may cause permanent damage).
Voltage Depression ("Memory Effect") from repeated partial discharge can occur, but is reversible through charge cycling.[1]
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) 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.
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.
NiMH has a somewhat higher self-discharge rate than NiCd in the past, which is no more true at present time. The self-discharge is 5-10% on the first day[2], and stabilizes around 0.5-1% per day at room temperature. 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 discharge rates.
A new type of nickel-metal hydride battery was introduced in 2006 that claims to reduce self-discharge, and therefore lengthen shelf life. By using a new separator, manufacturers claim between 70 to 85% of capacity is retained after one year, when stored at 20 degrees Celsius (68F). These cells are marketed as "ready-to-use" rechargeables, and are targeted towards typical consumers who use their digital cameras only a few times a year. 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 (May 2007) are Accupower Acculoop, Ansmann MaxE range, Gold Peak ReCyko, Kodak Pre Charged, Nexcell EnergyOn, Panasonic R2, Rayovac Hybrid, Sanyo Eneloop, Titanium Power Enduro, Uniross Hybrio, and VARTA Ready2use. These appear to be available in AA and AAA sizes only, and have less capacity (2000~2100mAh in AA) than the current generation of high-capacity cells (2800mAh, AA).
Cadmium is poisonous, so NiMH batteries are less detrimental to the environment than NiCd batteries.
Battery recycling programs exist to take care of end-of-life batteries.
Another issue is the environmental impact of nickel mines.
NiMH batteries and chargers are readily available in retail stores in common sizes: AAA, AA, C and D.
They 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 applications are 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 3000mAh capacity under low current demand (200mA), will have less than 1000mAh capacity under 1000mA (reference). Digital cameras with LCDs and flashlights can draw over 1A, quickly depleting Alkaline batteries after 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 disposable batteries at equivalent sizes. Even though the voltage is lower, it can be beneficial 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.
Lithium ion batteries are more compact than nickel-metal hydride batteries.[3]
Metal hydrides are relatively safe materials for energy storage. However, a seldom cycle reaction (Kühne effect) may lead to the pulverization and explosion of the metal hydride.
When hydrogen is absorbed by metals, then it forms bubbles around impurities and lattice defects of the metal. During their growth until a diameter of several micrometers, the bubbles deform the metal lattice and create mechanical stresses. After several hours, the mechanical stresses have become strong enough to create cracks which propagate through the metal lattice. The cracks are formed preferentially between the hydride bubbles and the weaker hydrided metal. Palladium dihydride is a semi-metal. Therefore the different electronegativities of metal and hydrogen generate positively electrically charged hydride bubble surfaces. Hence, the crack sides become electrically charged. Within the cracks of typically one micrometer width and ten to hundred micrometers length there arises an electric field strength of one hundred million volts per centimeter. Within strongly hydrided metals, electrons are bound stronger than hydrogen nuclei. Therefore the electric field within the cracks allows the hydrogen nuclei of the bubbles to accelerate until they reach energies of typically ten kilo-electron-volts.
Within the weaker hydrided metal, the hydrogen nuclei transfer their kinetic energy of several kilo-electron-volts to the metal lattice during a path of one tenth of a micrometer. This energy transfer creates hot spots within the hydrided metal with a mean temperature of typically ten thousand degrees Celsius and a pressure of ten billion Pascal. Within the hot spots, the hydrided metal is gaseous. Because of the high internal pressure, the hot spots transfer their heat energy explosively to the surrounding solid hydrided metal, where the explosions generate further cracks. When such a crack collides with the surface of a hydrided bubble, then the electrically charged bubble surface generates a strong electric field within the crack. Again, the electric field accelerates hydrogen nuclei from the bubble until they get several kilo-electron-volts of energy. Hence, a cycle reaction of the creation of cracks, electric fields, kilo-electron-volt hydrogen nuclei, hot spots, and micro-explosions is generated. This cycle reaction might result in the pulverization and even explosion of the entire metal hydride.
★ "Bipolar Nickel Metal Hydride Battery" by Martin G. Klein, Michael Eskra, Robert Plivelich and Paula Ralston
★ "The possible hot nature of cold fusion", by Rainer W. Kühne, in: ''Fusion Technology'' 25, 198–202 (1994)
1. Voltage Depression ("Memory Effect")
2. What's the Best Battery?
3. Mitsubishi Heavy to make lithium ion car batteries
★ BatteryUniversity.com
★ Battery Care & Tips
★ Duracell Ni-MH Technical Bulletin
★ Energizer Ni-MH Battery Datasheets
A 'nickel-metal hydride battery', abbreviated 'NiMH', is a type of rechargeable battery similar to a nickel-cadmium (NiCd) battery but has a hydrogen-absorbing alloy for the anode instead of cadmium. Like in NiCd batteries, nickel is the cathode. A NiMH battery can have two to three times the capacity of an equivalent size NiCd and the memory effect is not as significant. 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 capacities ''C'' ranging from 1100 mA·h to 2700 mA·h at 1.2 V, usually rated at 0.2×''C'' rate. Useful discharge capacity is an inverse function of the discharge rate, but up to around 1×''C'' rate, there is no significant difference.
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).
Modern, high capacity NiMH rechargeable batteries
| Contents |
| History |
| Applications |
| Electrochemistry |
| Charging |
| Discharging |
| Self-discharge |
| Low Self Discharge Batteries |
| Environment |
| Comparison with other battery types |
| Security and Danger |
| References |
| External links |
History
NiMH battery technology was developed at the end of the 1980s and commercialised first by the Matsushita Company .
Applications
Applications of NiMH type batteries includes 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 and RC cars.
Electrochemistry
The anode reaction occurring in a NiMH battery is as follows:
H2O + M + e− ↔ OH− + M-H
The battery is charged in the right direction of this equation and discharged in the left direction.
Nickel(II) hydroxide forms the cathode.
The "metal" in the anode 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 hydrogen ions are forced out of the potassium hydroxide electrolyte solution by the voltage applied during charging, this process prevents them from forming a gas, allowing a low pressure and volume to be maintained. As the battery is discharged, these same ions are released to participate in the reverse reaction.
NiMH batteries have an alkaline electrolyte, usually potassium hydroxide.
Charging
NIMH Charge curve
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 1.2V during discharge, down to about 1.0V (further discharge may cause permanent damage).
Voltage Depression ("Memory Effect") from repeated partial discharge can occur, but is reversible through charge cycling.[1]
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) 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.
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 has a somewhat higher self-discharge rate than NiCd in the past, which is no more true at present time. The self-discharge is 5-10% on the first day[2], and stabilizes around 0.5-1% per day at room temperature. 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 discharge rates.
Low Self Discharge Batteries
A new type of nickel-metal hydride battery was introduced in 2006 that claims to reduce self-discharge, and therefore lengthen shelf life. By using a new separator, manufacturers claim between 70 to 85% of capacity is retained after one year, when stored at 20 degrees Celsius (68F). These cells are marketed as "ready-to-use" rechargeables, and are targeted towards typical consumers who use their digital cameras only a few times a year. 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 (May 2007) are Accupower Acculoop, Ansmann MaxE range, Gold Peak ReCyko, Kodak Pre Charged, Nexcell EnergyOn, Panasonic R2, Rayovac Hybrid, Sanyo Eneloop, Titanium Power Enduro, Uniross Hybrio, and VARTA Ready2use. These appear to be available in AA and AAA sizes only, and have less capacity (2000~2100mAh in AA) than the current generation of high-capacity cells (2800mAh, AA).
Environment
Cadmium is poisonous, so NiMH batteries are less detrimental to the environment than NiCd batteries.
Battery recycling programs exist to take care of end-of-life batteries.
Another issue is the environmental impact of nickel mines.
Comparison with other battery types
NiMH batteries and chargers are readily available in retail stores in common sizes: AAA, AA, C and D.
They 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 applications are 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 3000mAh capacity under low current demand (200mA), will have less than 1000mAh capacity under 1000mA (reference). Digital cameras with LCDs and flashlights can draw over 1A, quickly depleting Alkaline batteries after 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 disposable batteries at equivalent sizes. Even though the voltage is lower, it can be beneficial 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.
Lithium ion batteries are more compact than nickel-metal hydride batteries.[3]
Security and Danger
Metal hydrides are relatively safe materials for energy storage. However, a seldom cycle reaction (Kühne effect) may lead to the pulverization and explosion of the metal hydride.
When hydrogen is absorbed by metals, then it forms bubbles around impurities and lattice defects of the metal. During their growth until a diameter of several micrometers, the bubbles deform the metal lattice and create mechanical stresses. After several hours, the mechanical stresses have become strong enough to create cracks which propagate through the metal lattice. The cracks are formed preferentially between the hydride bubbles and the weaker hydrided metal. Palladium dihydride is a semi-metal. Therefore the different electronegativities of metal and hydrogen generate positively electrically charged hydride bubble surfaces. Hence, the crack sides become electrically charged. Within the cracks of typically one micrometer width and ten to hundred micrometers length there arises an electric field strength of one hundred million volts per centimeter. Within strongly hydrided metals, electrons are bound stronger than hydrogen nuclei. Therefore the electric field within the cracks allows the hydrogen nuclei of the bubbles to accelerate until they reach energies of typically ten kilo-electron-volts.
Within the weaker hydrided metal, the hydrogen nuclei transfer their kinetic energy of several kilo-electron-volts to the metal lattice during a path of one tenth of a micrometer. This energy transfer creates hot spots within the hydrided metal with a mean temperature of typically ten thousand degrees Celsius and a pressure of ten billion Pascal. Within the hot spots, the hydrided metal is gaseous. Because of the high internal pressure, the hot spots transfer their heat energy explosively to the surrounding solid hydrided metal, where the explosions generate further cracks. When such a crack collides with the surface of a hydrided bubble, then the electrically charged bubble surface generates a strong electric field within the crack. Again, the electric field accelerates hydrogen nuclei from the bubble until they get several kilo-electron-volts of energy. Hence, a cycle reaction of the creation of cracks, electric fields, kilo-electron-volt hydrogen nuclei, hot spots, and micro-explosions is generated. This cycle reaction might result in the pulverization and even explosion of the entire metal hydride.
References
★ "Bipolar Nickel Metal Hydride Battery" by Martin G. Klein, Michael Eskra, Robert Plivelich and Paula Ralston
★ "The possible hot nature of cold fusion", by Rainer W. Kühne, in: ''Fusion Technology'' 25, 198–202 (1994)
1. Voltage Depression ("Memory Effect")
2. What's the Best Battery?
3. Mitsubishi Heavy to make lithium ion car batteries
External links
★ BatteryUniversity.com
★ Battery Care & Tips
★ Duracell Ni-MH Technical Bulletin
★ Energizer Ni-MH Battery Datasheets
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