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Nickel–metal hydride battery

(Redirected fromNickel–metal hydride)
"NiMH" redirects here. For other uses, seeNIMH.
Not to be confused withnickel–hydrogen battery.

Anickel–metal hydride battery(NiMHorNi–MH) is a type ofrechargeable battery.The chemical reaction at the positive electrode is similar to that of thenickel–cadmium cell(NiCd), with both usingnickel oxide hydroxide(NiOOH). However, the negative electrodes use a hydrogen-absorbingalloyinstead ofcadmium.NiMH batteries can have two to three times the capacity of NiCd batteries of the same size, with significantly higherenergy density,although only about half that oflithium-ion batteries.[6]

Nickel–metal hydride battery
Modern Ni–MH rechargeable cells
Specific energy0.22-0.43MJ/kg(60–120W·h/kg)
Energy density140–300 W·h/L
Specific power250–1,000 W/kg
Charge/discharge efficiency66%[1]–92%[2]
Self-discharge ratePer month:
  • 13.9–70.6% atroom temperature
  • 36.4–97.8% at 45 °C (113 °F)
  • Low self-discharge: 0.08–2.9%[3]
Cycle durability180[4]–2000[5]cycles
Nominal cell voltage1.2 V

They are typically used as a substitute for similarly shaped non-rechargeablealkaline batteries,as they feature a slightly lower but generally compatible cell voltage and are less prone toleaking.[7][8]

History

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Disassembled NiMHAA battery:
  1. Positive terminal
  2. Outer metal casing (also negative terminal)
  3. Positive electrode
  4. Negative electrode with current collector (metal grid, connected to metal casing)
  5. Separator (between electrodes)
See also:History of the battery

Work on NiMH batteries began at theBattelle-Geneva Research Center following the technology's invention in 1967. It was based onsinteredTi2Ni+TiNi+x alloys and NiOOH electrodes. Development was sponsored over nearly two decades byDaimler-Benzand byVolkswagen AGwithin Deutsche Automobilgesellschaft, now a subsidiary ofDaimler AG.The batteries' specific energy reached 50 W·h/kg (180 kJ/kg), specific power up to 1000 W/kg and a life of 500charge cycles(at 100%depth of discharge).Patentapplications were filed in European countries (priority: Switzerland), the United States, and Japan. The patents transferred to Daimler-Benz.[9]

Interest grew in the 1970s with the commercialisation of thenickel–hydrogen batteryfor satellite applications. Hydride technology promised an alternative, less bulky way to store the hydrogen. Research carried out byPhilips Laboratoriesand France'sCNRSdeveloped new high-energy hybrid alloys incorporatingrare-earth metalsfor the negative electrode. However, these suffered from alloy instability inalkalineelectrolyteand consequently insufficient cycle life. In 1987, Willems and Buschow demonstrated a successful battery based on this approach (using a mixture of La0.8Nd0.2Ni2.5Co2.4Si0.1), which kept 84% of its charge capacity after 4000 charge-discharge cycles. More economically viable alloys usingmischmetalinstead oflanthanumwere soon developed. Modern NiMH cells were based on this design.[10]The first consumer-grade NiMH cells became commercially available in 1989.[11]

In 1998,Stanford OvshinskyatOvonic Battery Co.,which had been working on MH-NiOOH batteries since mid-1980,[12]improved the Ti–Ni alloy structure and composition and patented its innovations.[13]

In 2008, more than two million hybrid cars worldwide were manufactured with NiMH batteries.[14]

In the European Union due to itsBattery Directive,nickel–metal hydride batteries replaced Ni–Cd batteries for portable consumer use.[15]

About 22% of portable rechargeable batteries sold in Japan in 2010 were NiMH.[16]In Switzerland in 2009, the equivalent statistic was approximately 60%.[17]This percentage has fallen over time due to the increase in manufacture oflithium-ionbatteries: in 2000, almost half of all portable rechargeable batteries sold in Japan were NiMH.[16]

In 2015BASFproduced a modified microstructure that helped make NiMH batteries more durable, in turn allowing changes to the cell design that saved considerable weight, allowing the specific energy to reach 140 watt-hours per kilogram.[18]

Electrochemistry

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The negative electrode reaction occurring in a NiMH cell is

H2O + M + e−⇌ OH−+ MH

On the positive electrode, nickel oxyhydroxide, NiO(OH), is formed:

Ni(OH)2+ OH−⇌ NiO(OH) + H2O + e−

The reactions proceed left to right during charge and the opposite during discharge. The metal M in the negative electrode of a NiMH cell is anintermetalliccompound. 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 arare-earthmixture oflanthanum,cerium,neodymium,praseodymium,and B isnickel,cobalt,manganese,oraluminium.Some cells use higher-capacity negative electrode materials based on AB2compounds, where A is titanium orvanadium,and B iszirconiumor nickel, modified withchromium,cobalt,iron,ormanganese.[19]

NiMH cells have analkalineelectrolyte,usuallypotassium hydroxide.The positive electrode is nickel hydroxide, and the negative electrode is hydrogen in the form of an interstitial metal hydride.[20]Hydrophilicpolyolefinnonwovens are used for separation.[21]

Charge

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When fast-charging, it is advisable to charge the NiMH cells with a smartbattery chargerto avoidovercharging,which can damage cells.[22]

Trickle charging

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The simplest of the safe charging methods is with a fixed low current, with or without a timer. Most manufacturers claim that overcharging is safe at very low currents, below 0.1C(C/10) (whereCis the current equivalent to the capacity of the battery divided by one hour).[23]The Panasonic NiMH charging manual warns that overcharging for long enough can damage a battery and suggests limiting the total charging time to 10–20 hours.[22]

Duracell further suggests that a trickle charge atC/300 can be used for batteries that must be kept in a fully charged state.[23]Some chargers do this after the charge cycle, to offset natural self-discharge. A similar approach is suggested by Energizer,[20]which indicates that self-catalysis can recombine gas formed at the electrodes for charge rates up to C/10. This leads to cell heating. The company recommendsC/30 orC/40 for indefinite applications where long life is important. This is the approach taken in emergency lighting applications, where the design remains essentially the same as in older NiCd units, except for an increase in the trickle-charging resistor value.[citation needed]

Panasonic's handbook recommends that NiMH batteries on standby be charged by a lowerduty cycleapproach, where a pulse of a higher current is used whenever the battery's voltage drops below 1.3 V. This can extend battery life and use less energy.[22]

ΔVcharging method

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NiMH charge curve

To prevent cell damage, fast chargers must terminate their charge cycle before overcharging occurs. One method is to monitor the change of voltage with time. When the battery is fully charged, the voltage across its terminals drops slightly. The charger can detect this and stop charging. This method is often used with nickel–cadmium cells, which display a large voltage drop at full charge. However, the voltage drop is much less pronounced for NiMH and can be non-existent at low charge rates, which can make the approach unreliable.[23]

Another option is to monitor the change of voltage with respect to time and stop when this becomes zero, but this risks premature cutoffs.[23]With this method, a much higher charging rate can be used than with a trickle charge, up to 1C.At this charge rate, Panasonic recommends to terminate charging when the voltage drops 5–10 mV per cell from the peak voltage.[22]Since this method measures the voltage across the battery, a constant-current (rather than a constant-voltage) charging circuit is used.

ΔTcharging method

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The temperature-change method is similar in principle to the ΔVmethod. Because the charging voltage is nearly constant, constant-current charging delivers energy at a near-constant rate. When the cell is not fully charged, most of this energy is converted to chemical energy. However, when the cell reaches full charge, most of the charging energy is converted to heat. This increases the rate of change of battery temperature, which can be detected by a sensor such as athermistor.Both Panasonic and Duracell suggest a maximal rate of temperature increase of 1 °C per minute. Using a temperature sensor allows an absolute temperature cutoff, which Duracell suggests at 60 °C.[23]With both the ΔTand the ΔVcharging methods, both manufacturers recommend a further period of trickle charging to follow the initial rapid charge.[citation needed]

Safety

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NiMH cell that popped its cap due to failed safety valve

Aresettable fusein series with the cell, particularly of thebimetallic striptype, increases safety. This fuse opens if either the current or the temperature gets too high.[23]

Modern NiMH cells contain catalysts to handle gases produced by over-charging:

However, this only works withoverchargingcurrentsof up to 0.1C(that is,nominal capacitydivided by ten hours). This reaction causes batteries to heat, ending the charging process.[23]

A method for very rapid charging calledin-cell charge controlinvolves an internal pressure switch in the cell, which disconnects the charging current in the event of overpressure.

One inherent risk with NiMH chemistry is that overcharging causes hydrogen gas to form, potentially rupturing the cell. Therefore, cells have a vent to release the gas in the event of serious overcharging.[24]

NiMH batteries are made of environmentally friendly materials.[25]The batteries contain only mildly toxic substances and are recyclable.[20]

Loss of capacity

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Voltage depression(often mistakenly attributed to thememory effect) from repeated partial discharge can occur, but is reversible with a few full discharge/charge cycles.[26]

Discharge

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A fully charged cell supplies an average 1.25 V/cell during discharge, declining to about 1.0–1.1 V/cell (further discharge may cause permanent damage in the case of multi-cell packs, due to polarity reversal of the weakest cell). Under a light load (0.5 amperes), the starting voltage of a freshly chargedAANiMH cell in good condition is about 1.4 volts.[27]

Over-discharge

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Complete discharge of multi-cell packs can causereverse polarityin one or more cells, which can permanently damage them. This situation can occur in the common arrangement of four AA cells in series, where one cell completely discharges before the others due to small differences in capacity among the cells. When this happens, the good cells start to drive the discharged cell into reverse polarity (i.e. positive anode and negative cathode). Some cameras,GPS receiversandPDAsdetect the safe end-of-discharge voltage of the series cells and perform an auto-shutdown, but devices such as flashlights and some toys do not.

Irreversible damage from polarity reversal is a particular danger, even when a low voltage-threshold cutout is employed, when the cells vary in temperature. This is because capacity significantly declines as the cells are cooled. This results in a lower voltage under load of the colder cells.[28]

Self-discharge

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Historically, NiMH cells have had a somewhat higherself-dischargerate (equivalent to internal leakage) than NiCd cells. The self-discharge rate varies greatly with temperature, where lower storage temperature leads to slower discharge and longer battery life. The self-discharge is5–20%on the first day and stabilizes around0.5–4%per day atroom temperature.[29][30][31][32][33]But at 45 °C (113 °F) it is approximately three times as high.[23]

Low self-discharge

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Thelow–self-discharge nickel–metal hydride battery(LSD NiMH) has a significantly lower rate of self-discharge. The innovation was introduced in 2005 bySanyo,brandedEneloop.[34]By using improvements to electrode separator, positive electrode, and other components, manufacturers claim the cells retain 70–85% of their capacity when stored for one year at 20 °C (68 °F), compared to about half for normal NiMH batteries. They are otherwise similar to standard NiMH batteries, and can be charged in standard NiMH chargers. These cells are marketed as "hybrid", "ready-to-use" or "pre-charged" rechargeables. Retention of charge depends in large part on the battery'sleakageresistance (the higher the better), and on its physical size and charge capacity.

Separatorskeep the two electrodes apart to slow electrical discharge while allowing the transport of ioniccharge carriersthat close the circuit during the passage ofcurrent.[35]High-quality separators are critical for battery performance.

The self-discharge rate depends upon separator thickness; thicker separators reduce self-discharge, but also reduce capacity as they leave less space for active components, and thin separators lead to higher self-discharge. Some batteries may have overcome thistradeoffby using more precisely manufactured thin separators, and a sulfonated polyolefin separator, an improvement over the hydrophilic polyolefin based onethylene vinyl alcohol.[36]

Low-self-discharge cells have somewhat lower capacity than otherwise equivalent NiMH cells because of the larger volume of the separator. The highest-capacity low-self-discharge AA cells have 2500 mAh capacity, compared to 2700 mAh for high-capacity AA NiMH cells.[37]

Common methods to improve self-discharge include: use of a sulfonated separator (causing removal of N-containing compounds), use of an acrylic acid grafted PP separator (causing reduction in Al- and Mn-debris formation in separator), removal of Co and Mn in A2B7MH alloy, (causing reduction in debris formation in separator), increase of the amount of electrolyte (causing reduction in the hydrogen diffusion in electrolyte), removal of Cu-containing components (causing reduction in micro-short), PTFE coating on positive electrode (causing suppression of reaction between NiOOH and H2), CMC solution dipping (causing suppression of oxygen evolution), micro-encapsulation of Cu on MH alloy (causing decrease in H2released from MH alloy), Ni–B alloy coating on MH alloy (causing formation of a protection layer), alkaline treatment of negative electrode (causing reduction of leach-out of Mn and Al), addition of LiOH and NaOH into electrolyte (causing reduction in electrolyte corrosion capabilities), and addition of Al2(SO4)3into electrolyte (causing reduction in MH alloy corrosion). Most of these improvements have no or negligible effect on cost; some increase cost modestly.[38]

Compared to other battery types

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Alkaline batteries

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NiMH cells are often used in digital cameras and other high-drain devices, where over the duration of single-charge use they outperform primary (such as alkaline) batteries.

NiMH cells are advantageous for high-current-drain applications compared to alkaline batteries, largely due to their lower internal resistance. Typical alkaline AA-size batteries, which offer approximately 2.6 Ah capacity at low current demand (25 mA), provide only 1.3 Ah capacity with a 500 mA load.[39]Digital cameras with LCDs and flashlights can draw over 1 A, quickly depleting them. NiMH cells can deliver these current levels without similar loss of capacity.[20]

Devices that were designed to operate using primary alkaline chemistry (or zinc-carbon/chloride) cells may not function with NiMH cells. However, most devices compensate for the voltage drop of an alkaline battery as it discharges down to about 1 volt. Low internal resistance allows NiMH cells to deliver a nearly constant voltage until they are almost completely discharged. Thus battery-level indicators designed to read alkaline cells overstate the remaining charge when used with NiMH cells, as the voltage of alkaline cells decreases steadily during most of the discharge cycle.

Lithium-ion batteries

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Lithium-ion batteriescan deliver extremely high power and have a higher specific energy than nickel–metal hydride batteries,[40]but they were originally significantly more expensive.[41]The cost of lithium batteries fell drastically during the 2010s and many small consumer devices now have non-consumer-replaceable lithium batteries as a result. Lithium batteries produce a higher voltage (3.2–3.7 V nominal), and are thus not a drop-in replacement for AA (alkaline or NiMh) batteries without circuitry to reduce voltage. Although a single lithium cell will typically provide ideal power to replace 3 NiMH cells, the form factor means that the device still needs modification.

Lead Batteries

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NiMH batteries can easily be made smaller and lighter than lead-acid batteries and have completely replaced them in small devices. However, lead-acid batteries can deliver huge current at low cost, making lead-acid batteries more suitable for starter motors in combustion vehicles.

As of 2005,nickel–metal hydride batteries constituted three percent of the battery market.[25]

Applications

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High-power Ni–MH battery ofToyota NHW20 Prius,Japan
nickel–metal hydride 24 V battery pack made byVARTA,Museum Autovision,Altlussheim,Germany

Consumer electronics

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NiMH batteries have replaced NiCd for many roles, notably small rechargeable batteries. NiMH batteries are commonly available in AA (penlight-size) batteries. These have nominal charge capacities (C) of 1.1–2.8 Ah at 1.2 V, measured at the rate that discharges the cell in 5 hours. Useful discharge capacity is a decreasing function of the discharge rate, but up to a rate of around 1×C(full discharge in 1 hour), it does not differ significantly from the nominal capacity.[26]NiMH batteries nominally operate at 1.2 V per cell, somewhat lower than conventional 1.5 V cells, but can operate many devices designed for thatvoltage.

Electric vehicles

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Main articles:Electric vehicle,Battery electric vehicle,Who Killed the Electric Car?,Electric car,andPatent encumbrance of large automotive NiMH batteries
GM Ovonic NiMH Battery Module

NiMH batteries were frequently used in prior-generation electric and hybrid-electric vehicles; as of 2020 they have been superseded almost entirely by lithium-ion batteries in all-electric and plug-in hybrid vehicles, but they remain in use in some hybrid vehicles (2020 Toyota Highlander, for example).[42]Prior all-electric plug-in vehicles included theGeneral Motors EV1,first-generationToyota RAV4 EV,Honda EV Plus,Ford Ranger EVandVectrixscooter. Every first generationhybrid vehicleused NIMH batteries, most notably theToyota PriusandHonda Insight,as well as later models including theFord Escape Hybrid,Chevrolet Malibu HybridandHonda Civic Hybridalso use them.

Patent issues

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Stanford R. Ovshinskyinvented and patented a popular improvement of the NiMH battery and foundedOvonic Battery Companyin 1982.General Motorspurchased Ovonics' patent in 1994. By the late 1990s, NiMH batteries were being used successfully in many fully electric vehicles, such as theGeneral Motors EV1andDodge Caravan EPICminivan.

This generation of electric cars, although successful, was abruptly pulled off the market.[citation needed]

In October 2000, the patent was sold toTexaco,and a week later Texaco was acquired byChevron.Chevron'sCobasyssubsidiary provides these batteries only to large OEM orders. General Motorsshut down production of the EV1,citing lack of battery availability as a chief obstacle. Cobasys control of NiMH batteries created a patent encumbrance for large automotive NiMH batteries.[43][44][45][46][47]

See also

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References

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  1. ^"NiMH Battery Charging Basics".PowerStream.
  2. ^"Energy efficiency and capacity retention of Ni–MH batteries for storage applications".
  3. ^"Best rechargeable batteries (10+ charts, overviews and comparisons )".eneloop101.14 February 2017.Retrieved2019-02-09.
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  6. ^"Lithium-Ion Battery".Clean Energy Institute, University of Washington.Retrieved8 January2021.
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  9. ^The US patent isUS patent 3824131A,Dr. Klaus Beccu, "Negative electrode of titanium-nickel alloy hydride phases", assigned to Battelle-Geneva R&D Center.For the performance data, see the "Examples" section.
  10. ^Nii, K.; Amano, M. (1997)."R & D of Hydrogen Absorbing Alloys in Japan".Acta Metallurgica Sinica.10(3): 249–255.Retrieved10 September2011.
  11. ^In search of the perfect battery,The Economist,6 March 2008.
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  13. ^US patent 6413670,"High power nickel metal hydride batteries and high power alloys/electrodes for use therein", published July 2, 2002
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  30. ^"epanorama.net: Battery Power Supply Page".Retrieved2009-07-10.A NiMH battery can lose up to 2% of its charge per day sitting on the shelf.
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  33. ^"GP Batteries (Hong Kong) FAQ".Archived fromthe originalon 2007-12-11.Retrieved2009-07-10.18. 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.
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  36. ^Shinyama, Katsuhiko; Harada, Yasuyuki; Maeda, Reizo; Nakamura, Hiroshi; Matsuta, Shigeki; Nohma, Toshiyuki; Yonezu, Ikuo (May 2006). "Suppression mechanism of the self-discharge reaction in nickel–metal hydride batteries using a sulfonated polyolefin separator".Research on Chemical Intermediates.32(5): 453–459.doi:10.1163/156856706777973673.S2CID86865358.
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  38. ^Young, Kwo-hsiung; Yasuoka, Shigekazu (1 March 2016)."Capacity Degradation Mechanisms in Nickel/Metal Hydride Batteries".Batteries.2(1). MDPI AG: 3.doi:10.3390/batteries2010003.ISSN2313-0105.Table 3
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  45. ^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.ISBN978-0-679-42105-4.
  46. ^Coker, M. (2003-05-15)."Dude, Wheres My Electric Car!?!".OCWeekly.Archived fromthe originalon 2009-05-24.Retrieved2009-10-08.
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