How long do batteries last?
Created June 18, 2007, at 6:16 pm by Arizonagirl
We are seriously interested in a Civic Hybrid or Toyota Prius but we are worried about the cost of replacing the batteries. We keep our cars usually about 12 years so it's past the guarantee period I guess, but our mileage is less than 10,000 per year. Does anyone have any experience with replacing batteries? How long do they last? How much do they cost? Should we worry about this?



4 years ago
Clearly, the cars haven't been around for 12 years yet so it is hard to know what the situation will be then. Battery technology is getting much better and cheaper at about 10% per year over the past few decades so replacement is likely to be cheaper and better. One can also assume that after-market replacements are likely to come available but it is hard to tell if they will for today's models. Also, don't forget that the HCH will run, albeit underpowered, even if the traction battery is pretty weak.
I, too, generally try to run the wheels off of a car, pushing for 150K miles or more and 10 - 12 years before giving up on it. With our '03 HCH, we chose to get the 100K miles, 6 year, zero deductable, Honda extended warrantee in case there are any infant mortality problems in that time. Of course, that won't help with the last 6 years but at least it is a start. I'm kind of assuming we may have to deal with the batteries around 120K miles, just as one normally has to deal with the tranny, fuel pump, water pump, alternator, etc somewhere between 70K and 120K miles on an american built car.
In the case of hybrids, I guess that's the price of doing what's right. In the mean time, you get to enjoy the reduced grip that the oil companies have on you.
4 years ago
Arizonagirl:
Whichever car you pick (Civic or Prius) I'm sure you'll be satisfied in the long run. These two vehicles are the second generation rendition of the popular hybrid models, and they have been re-designed to promote long life and reliability.
Yes, the hybrid battery replacement cost question always seems to come up now and then. To mitigate that, both manufacturers have learnt alot and have done to utmost to extend the battery life by designing their systems so that long battery life is as long as possible. Both Honda and Toyota claim that the batteries will last the life of the car and they offer long warranties to support the "worst use case" scenarios. I would say that this goal still depends on driving conditions and total travelled distance, but for common drivers like us it is a non-issue.
Like you, I do not accummulate more than 10,000 miles a year and I keep my cars for a very long time (well beyond their warranties). As such, I am so confident in the technology that we now own a 2006 HCH, a 2007 Prius (Business car), and a 2007 HCH (wife's car) and I expect a very long and rewarding ownership for the years to come.
As time goes by, there will be battery replacements for some folks. The older the cars get the greater the statistical chance of that occurring. But, so do transmission replacements for almost every car, and a battery replacement is supposed to occur less often and cost about the same. In the case of the Prius, the eCVT transmission will literally last forever so there aren't many things to worry about with the car to begin with. Then you must also factor in the reduced wear on the components that most traditional cars need to have replaced regularly. This includes the brakes, gas engine, among other systems. Hybrids do not suffer at such rate and will save money in the longer run with reduced mechanical maintenance & failures.
Cheers;
MSantos
4 years ago
The way I see it is that with how civic is designed, the car will continue to work even the battery is dead since the motor is only assisting the engine. Of course, the car will perform just like a 90's civic base model with < 100 hp engine. I really doubt that Toyota Prius can do that without a battery since I read that it is driven by the motor and assisted by the gas engine.
4 years ago
Toyota has been selling the Prius in the US since 1999. Same for the Honda Insight (2000 model year).
Find an early model for sale with 100,000 miles (10 years equivalent for you) and test drive it. That'll tell you how well the batteries hold up over time.
4 years ago
Partly so. The power-split device on the Prius can connect the gas engine directly to the wheels which makes it as much a parallel hybrid as the IMA system. However, on the issue of the battery: The main mitigating advantage for the Prius, is that the HSD battery pack is "more" engineered to make complete battery failures less likely. A NiMH pack on a Prius can report a bad cell/bank without affecting the overall battery functionality thus giving its owner the ability/opportunity to take corrective action before a total failure occurs.
On the HCH-2 the battery pack health is monitored as a collection of the entire cell count. This means that if one or more cells are faulty then there is no easy way to tell which they are unless they are evaluated individually - on the bench - which is time consuming and most shops will simply opt to replace the entire pack.
This is not to say that a Toyota dealership will not make the same replacement choice, but at least they have the option of faster troubleshooting and lower cost to the customer - especially if the bad cell count is low (this has happened already).
Still the probablility of a dead Prius exists if there's a significant problem with its hybrid's electric system. On a Civic Hybrid 2, the vehicle will still operate (although anemically) without its hybrid's electric system, so it would appear the HCH-2 could at least theoretically, have a slight edge in the unlikely event of such a complete battery failure.
Cheers;
MSantos
4 years ago
I have witnessed two Toyota`s with battery failures.
One was a 2004 and the other a 2005 with around 80K miles.
Toyota has updated the battery packs.:)
3 years ago
http://www.hybridcars.com/high-road/how-long-do-hybrid-batteries-last.ht...
check out this posting and see a prius that dies at 349,000 miles b/c of a kid running a red light..with same batteries. lots of into. fyi.
3 years ago
Honda has extended the warranty period on the Insight and HCH batteries to 100K miles. My 2000 Insight had a bad battery at 96K and my local dealer replaced the battery at NO Charge. It would have been about $2400 out of warranty. At 104K its running very well with exceptional MPG. Our 2003 HCH at 58K is running very well with no problems. I think the Honda hybrids are as reliable as non-hybrid Hondas.
1 year ago
I bought a 2003 Honda Civic Hybrid back in May 2002 and I currently have about 163k miles on the vehicle. I've gotten the IMA weak battery light turn on and the dealership has recommended a new battery, but my car is still running and I haven't noticed a great decrease in the battery strength. It does discharge and recharge more frequently, but I can still drive it and don't intend on spending money on a new battery unless I feel I can get another 100k+ out of the car with the new battery.
1 year ago
My civic is 8 years old and when I noticed the mileage was just not as goo,d I took it to the dealer. $3100 for a new battery. It is running fine and will do so until I get another car. Not worth replacing it. Won't buy a hybrid again and I was an ardent ecological driver. The oil change cost eat up your fuel savings. You can't take the car to a local mechanic as no one is trained on hybrids. Dealer maintenance is just too high. Looking at Jetta or Cooper now.
41 weeks ago
I am considering buying a used Ford Hybrid Escape with 84,000 miles. Wondering how long these batteries last? I understand the cost to replace is $5200. Also curious on the overall maintenance of these vehicles. The benefits out way the costs. It's a moral dilemma on Earth Day. Ecology or Economy?
35 weeks ago
vw's die die die.
i would not recomend getting one if u want it long term :/
35 weeks ago
I have a '96 Accord with 322K and have not had any problems with tranny, fuel pump, etc.
27 weeks ago
They lose 20% charge capacity per year, as per wiki article.
Lithium-ion battery
From Wikipedia, the free encyclopedia
(Redirected from Li Ion)
Not to be confused with Lithium battery or Lithium-ion polymer battery.
"Lithium-ion" redirects here. For the metal element, see Lithium.
Lithium-ion battery
Nokia Li-ion battery for powering a mobile phone
specific energy
100-250 W·h/kg [1]
(0.36-0.90 MJ/kg)
energy density
250-620 W·h/L [2]
(0.90-2.23 MJ/L)
specific power
~250-~340 W/kg[1]
Charge/discharge efficiency
80-90%[3]
Energy/consumer-price
2.5 W·h/US$[4]
Self-discharge rate
8% at 21 °C
15% at 40 °C
31% at 60 °C
(per month)[5]
Cycle durability
400-1200 cycles
[6]
Nominal cell voltage
3.6 / 3.7 V
A lithium-ion battery (sometimes Li-ion battery or LIB) is a family of rechargeable battery types in which lithium ions move from the negative electrode to the positive electrode during discharge, and back when charging. Chemistry, performance, cost, and safety characteristics vary across LIB types. Unlike lithium primary batteries (which are disposable), lithium-ion electrochemical cells use an intercalated lithium compound as the electrode material instead of metallic lithium.
Lithium-ion batteries are common in consumer electronics. They are one of the most popular types of rechargeable battery for portable electronics, with one of the best energy densities, no memory effect, and a slow loss of charge when not in use. Beyond consumer electronics, LIBs are also growing in popularity for military, electric vehicle, and aerospace applications.[7] Research is yielding a stream of improvements to traditional LIB technology, focusing on energy density, durability, cost, and intrinsic safety.
Lithium-ion batteries account for 67% of all portable secondary battery sales in Japan. In the UK lithium-ion batteries account for 4.3% of all portable battery sales and in the EU 1%. [8] [9] [10]
Contents
[hide] 1 Charge and discharge
2 Construction
3 Formats
4 History
5 Electrochemistry 5.1 Positive electrodes
5.2 Negative electrodes
5.3 Electrolytes
6 Advantages and disadvantages 6.1 Advantages
6.2 Disadvantages 6.2.1 Cell life
6.2.2 Internal resistance
6.2.3 Safety requirements
7 Specifications and design
8 Charging procedure
9 Variations in materials and construction
10 Usage guidelines 10.1 Prolonging battery pack life 10.1.1 Multicell devices
10.2 Safety 10.2.1 Recalls
10.2.2 Transport restrictions
11 Research
12 See also
13 Notes
14 References
15 External links
[edit] Charge and discharge
During discharge, lithium ions Li+ carry the current from the negative to the positive electrode, through the non-aqueous electrolyte and separator diaphragm.[11]
During charging, an external electrical power source (the charging circuit) applies a higher voltage (but of the same polarity) than that produced by the battery, forcing the current to pass in the reverse direction. The lithium ions then migrate from the positive to the negative electrode, where they become embedded in the porous electrode material in a process known as intercalation.
[edit] Construction
Cylindrical 18650 cell before closing
The three primary functional components of a lithium-ion battery are the anode, cathode, and electrolyte. The anode of a conventional lithium-ion cell is made from carbon, the cathode is a metal oxide, and the electrolyte is a lithium salt in an organic solvent.[12]
The most commercially popular anode material is graphite. The cathode is generally one of three materials: a layered oxide (such as lithium cobalt oxide), a polyanion (such as lithium iron phosphate), or a spinel (such as lithium manganese oxide).[13]
The electrolyte is typically a mixture of organic carbonates such as ethylene carbonate or diethyl carbonate containing complexes of lithium ions.[14] These non-aqueous electrolytes generally use non-coordinating anion salts such as lithium hexafluorophosphate (LiPF6), lithium hexafluoroarsenate monohydrate (LiAsF6), lithium perchlorate (LiClO4), lithium tetrafluoroborate (LiBF4), and lithium triflate (LiCF3SO3).
Depending on materials choices, the voltage, capacity, life, and safety of a lithium-ion battery can change dramatically. Recently, novel architectures using nanotechnology have been employed to improve performance.
Pure lithium is very reactive. It reacts vigorously with water to form lithium hydroxide and hydrogen gas. Thus, a non-aqueous electrolyte is typically used, and a sealed container rigidly excludes water from the battery pack.
Lithium ion batteries are more expensive than NiCd batteries but operate over a wider temperature range with higher energy densities, while being smaller and lighter. They are fragile and so need a protective circuit to limit peak voltages.
[edit] Formats
Nissan Leaf's lithium-ion battery pack.
Li-ion cells are available in various formats, which can generally be divided into four groups:[15]
Small cylindrical (solid body without terminals, such as those used in laptop batteries)
Large cylindrical (solid body with large threaded terminals)
Pouch (soft, flat body, such as those used in cell phones)
Prismatic (semi-hard plastic case with large threaded terminals, often used in vehicles' traction packs)
The lack of case gives pouch cells the highest energy density; however, pouch cells (and prismatic cells) require an external means of containment to prevent expansion when their SOC level is high.[16]
[edit] History
Varta Lithium-ion battery, Museum Autovision, Altlussheim, Germany
Lithium batteries were first proposed by M.S. Whittingham at Binghamton University, at Exxon, in the 1970s.[17] Whittingham used titanium(II) sulfide as the cathode and lithium metal as the anode.
The reversible intercalation in graphite[18][19] and intercalation into cathodic oxides [20][21] was also already discovered in the 1970s by J.O. Besenhard at TU Munich. He also proposed the application as high energy density Lithium cells[22][23]
Primary lithium batteries in which the anode is made from metallic lithium pose safety issues. As a result, lithium-ion batteries were developed in which both anode and cathode are made of a material containing lithium ions.
In 1979, John Goodenough demonstrated a rechargeable cell with high cell voltage in the 4V range using lithium cobalt oxide (LiCoO2) etc. as positive electrode and Lithium metal as negative electrode.[24] This innovation provided the positive electrode material which made the lithium-ion battery (LIB) possible. LiCoO2 is a stable positive electrode material which acts as a donor of Lithium ions, which meant that it could be used with negative electrode material other than Lithium metal. By enabling the use of stable and easy-to-handle negative electrode materials, LiCoO2 opened a whole new range of possibilities for novel rechargeable battery systems.
In 1981, Bell Labs developed a workable graphite anode[25] to provide an alternative to the lithium metal battery.
In 1982, Rachid Yazami demonstrated the reversible electrochemical intercalation of Lithium in graphite.[26][27] The organic electrolytes available at the time would decompose during charging if used with graphite negative electrode, preventing the early development of a rechargeable battery which employed the Lithium/graphite system. Yazami used a solid electrolyte to demonstrate that Lithium could be reversibly intercalated in graphite through an electrochemical mechanism.
In 1983, Dr. Michael Thackeray, Goodenough, and coworkers identified manganese spinel as a cathode material.[28] Spinel showed great promise, given low-cost, good electronic and lithium ion conductivity, and three-dimensional structure which gives it good structural stability. Although pure manganese spinel fades with cycling, this can be overcome with chemical modification of the material.[29] Manganese spinel is currently used in commercial cells.[30]
In 1985, Akira Yoshino assembled a prototype cell using as anode a certain carbonaceous material into which lithium ions could be inserted and as cathode lithium cobalt oxide (LiCoO2) etc. which is stable in air.[31] By using an anode material without metallic lithium, safety was dramatically improved over batteries which used lithium metal. The use of lithium cobalt oxide (LiCoO2) enabled industrial-scale production to be achieved easily.
This was the birth of the current lithium-ion battery.
Then in 1991, Sony and Asahi Kasei released the first commercial lithium-ion battery.
In 1989, Goodenough and Arumugam Manthiram of the University of Texas at Austin showed that cathodes containing polyanions, e.g. sulfates, produce higher voltages than oxides due to the inductive effect of the polyanion.[32]
In 1996, Goodenough, Akshaya Padhi and coworkers identified lithium iron phosphate (LiFePO4) and other phospho-olivines (lithium metal phosphates with olivine structure) as cathode materials.[33]
In 2002, Yet-Ming Chiang and his group at MIT showed a substantial improvement in the performance of lithium batteries by boosting the material's conductivity by doping it with aluminum, niobium and zirconium. The exact mechanism causing the increase became the subject of a debate.[34]
In 2004, Chiang again increased performance by utilizing iron-phosphate particles of less than 100 nanometers in diameter. This decreased particle density by almost one hundredfold, increased the cathode's surface area and improved capacity and performance. Commercialization led to a competitive market and a patent infringement battle between Chiang and Goodenough.[34]
[edit] Electrochemistry
The three participants in the electrochemical reactions in a lithium-ion battery are the anode, cathode, and electrolyte.
Both the anode and cathode are materials into which, and from which, lithium can migrate. During insertion (or intercalation) lithium moves into the electrode. During the reverse process, extraction (or deintercalation), lithium moves back out. When a lithium-based cell is discharging, the lithium is extracted from the anode and inserted into the cathode. When the cell is charging, the reverse occurs.
Useful work can only be extracted if electrons flow through a closed external circuit. The following equations are in units of moles, making it possible to use the coefficient x.
The positive electrode half-reaction (with charging being forwards) is: [35]
The negative electrode half-reaction is:
The overall reaction has its limits. Overdischarge supersaturates lithium cobalt oxide, leading to the production of lithium oxide,[36] possibly by the following irreversible reaction:
Overcharge up to 5.2 Volts leads to the synthesis of cobalt(IV) oxide, as evidenced by x-ray diffraction[37]
In a lithium-ion battery the lithium ions are transported to and from the cathode or anode, with the transition metal, cobalt (Co), in LixCoO2 being oxidized from Co3+ to Co4+ during charging, and reduced from Co4+ to Co3+ during discharge.
[edit] Positive electrodes
Electrode material
Average potential difference
Specific capacity
Specific energy
LiCoO2
3.7 V
140 mA·h/g
0.518 kW·h/kg
LiMn2O4
4.0 V
100 mA·h/g
0.400 kW·h/kg
LiNiO2
3.5 V
180 mA·h/g
0.630 kW·h/kg
LiFePO4
3.3 V
150 mA·h/g
0.495 kW·h/kg
Li2FePO4F
3.6 V
115 mA·h/g
0.414 kW·h/kg
LiCo1/3Ni1/3Mn1/3O2
3.6 V
160 mA·h/g
0.576 kW·h/kg
Li(LiaNixMnyCoz)O2
4.2 V
220 mA·h/g
0.920 kW·h/kg
[edit] Negative electrodes
Electrode material
Average potential difference
Specific capacity
Specific energy
Graphite (LiC6)
0.1-0.2 V
372 mA·h/g
0.0372-0.0744 kW·h/kg
Hard Carbon (LiC6)
? V
? mA·h/g
? kW·h/kg
Titanate (Li4Ti5O12)
1-2 V
160 mA·h/g
0.16-0.32 kW·h/kg
Si (Li4.4Si)[38]
0.5-1 V
4212 mA·h/g
2.106-4.212 kW·h/kg
Ge (Li4.4Ge)[39]
0.7-1.2 V
1624 mA·h/g
1.137-1.949 kW·h/kg
[edit] Electrolytes
The cell voltages given in the Electrochemistry section are larger than the potential at which aqueous solutions can electrolyze, in addition lithium is highly reactive to water, therefore, nonaqueous or aprotic solutions are used.
Liquid electrolytes in lithium-ion batteries consist of lithium salts, such as LiPF6, LiBF4 or LiClO4 in an organic solvent, such as ethylene carbonate, dimethyl carbonate, and diethyl carbonate. A liquid electrolyte conducts lithium ions, acting as a carrier between the cathode and the anode when a battery passes an electric current through an external circuit. Typical conductivities of liquid electrolyte at room temperature (20 °C (68 °F)) are in the range of 10 mS/cm (1 S/m), increasing by approximately 30–40% at 40 °C (104 °F) and decreasing by a slightly smaller amount at 0 °C (32 °F)[40]
Unfortunately, organic solvents easily decompose on anodes during charging. However, when appropriate organic solvents are used as the electrolyte, the solvent decomposes on initial charging and forms a solid layer called the solid electrolyte interphase (SEI),[41] which is electrically insulating yet provides sufficient ionic conductivity. The interphase prevents decomposition of the electrolyte after the second charge. For example, ethylene carbonate is decomposed at a relatively high voltage, 0.7 V vs. lithium, and forms a dense and stable interface.[citation needed]
A good solution for the interface instability is the application of a new class of composite electrolytes based on POE (poly(oxyethylene)) developed by Syzdek et al.[42][43] It can be either solid (high molecular weight) and be applied in dry Li-polymer cells, or liquid (low molecular weight) and be applied in regular Li-ion cells.
Another issue that Li-ion technology is facing is safety. Large scale application of Li cells in Electric Vehicles needs a dramatic decrease in the failure rate. One of the solutions is the novel technology based on reversed-phase composite electrolytes, employing porous ceramic material filled with electrolyte.[44]
[edit] Advantages and disadvantages
Note that both advantages and disadvantages depend on the materials and design that make up the battery. This summary reflects older designs that use carbon anode, metal oxide cathodes, and lithium salt in an organic solvent for the electrolyte.
[edit] Advantages
A lithium-ion battery from a laptop computer Wide variety of shapes and sizes efficiently fitting the devices they power.
Much lighter than other energy-equivalent secondary batteries.[45]
High open circuit voltage in comparison to aqueous batteries (such as lead acid, nickel-metal hydride and nickel-cadmium).[46] This is beneficial because it increases the amount of power that can be transferred at a lower current.
No memory effect.
Self-discharge rate of approximately 5-10% per month, compared to over 30% per month in common nickel metal hydride batteries, approximately 1.25% per month for Low Self-Discharge NiMH batteries and 10% per month in nickel-cadmium batteries.[47] According to one manufacturer, lithium-ion cells (and, accordingly, "dumb" lithium-ion batteries) do not have any self-discharge in the usual meaning of this word.[35] What looks like a self-discharge in these batteries is a permanent loss of capacity (see Disadvantages). On the other hand, "smart" lithium-ion batteries do self-discharge, due to the drain of the built-in voltage monitoring circuit.
Components are environmentally safe as there is no free lithium metal.[citation needed]
[edit] Disadvantages
[edit] Cell life
Charging forms deposits inside the electrolyte that inhibit ion transport. Over time, the cell's capacity diminishes. The increase in internal resistance reduces the cell's ability to deliver current. This problem is more pronounced in high-current applications. The decrease means that older batteries do not charge as much as new ones (charging time required decreases proportionally).
High charge levels and elevated temperatures (whether from charging or ambient air) hasten capacity loss.[48][49] Charging heat is caused by the carbon anode (typically replaced with lithium titanate which drastically reduces damage from charging, including expansion and other factors).[50]
A Standard (Cobalt) Li-ion cell that is full most of the time at 25 °C (77 °F) irreversibly loses approximately 20% capacity per year. Poor ventilation may increase temperatures, further shortening battery life. Loss rates vary by temperature: 6% loss at 0 °C (32 °F), 20% at 25 °C (77 °F), and 35% at 40 °C (104 °F). When stored at 40%–60% charge level, the capacity loss is reduced to 2%, 4%, and 15%, respectively.[51][citation needed] In contrast, the calendar life of LiFePO4 cells is not affected by being kept at a high state of charge.[52]
[edit] Internal resistance
The internal resistance of standard (Cobalt) lithium-ion batteries is high compared to both other rechargeable chemistries such as nickel-metal hydride and nickel-cadmium, and LiFePO4 and lithium-polymer cells.[53] Internal resistance increases with both cycling and age.[49][54][55] Rising internal resistance causes the voltage at the terminals to drop under load, which reduces the maximum current draw. Eventually increasing resistance means that the battery can no longer operate for an adequate period.
To power larger devices, such as electric cars, connecting many small batteries in a parallel circuit is more effective[56] and efficient than connecting a single large battery.[57]
[edit] Safety requirements
If overheated or overcharged, Li-ion batteries may suffer thermal runaway and cell rupture.[58] In extreme cases this can lead to combustion. Deep discharge may short-circuit the cell, in which case recharging would be unsafe.[59] To reduce these risks, Lithium-ion battery packs contain fail-safe circuitry that shuts down the battery when its voltage is outside the safe range of 3–4.2 V per cell.[35][47] When stored for long periods the small current draw of the protection circuitry itself may drain the battery below its shut down voltage; normal chargers are then ineffective. Many types of lithium-ion cell cannot be charged safely below 0°C.[60]
Other safety features are required in each cell:[35]
shut-down separator (for overtemperature)
tear-away tab (for internal pressure)
vent (pressure relief)
thermal interrupt (overcurrent/overcharging)
These devices occupy useful space inside the cells, add additional points of failure and irreversibly disable the cell when activated. They are required because the anode produces heat during use, while the cathode may produce oxygen. These devices and improved electrode designs reduce/eliminate the risk of fire or explosion.
These safety features increase costs compared to nickel metal hydride batteries, which require only a hydrogen/oxygen recombination device (preventing damage due to mild overcharging) and a back-up pressure valve.[47]
[edit] Specifications and design
Specific energy density: 150 to 250 W·h/kg (540 to 900 kJ/kg)[1]
Volumetric energy density: 250 to 620 W·h/l (900 to 1900 J/cm³)[2]
Specific power density: 300 to 1500 W/kg (@ 20 seconds and 285 W·h/l)[1]
Because lithium-ion batteries can have a variety of cathode and anode materials, the energy density and voltage vary accordingly.
Lithium-ion batteries with a lithium iron phosphate cathode and graphite anode have a nominal open-circuit voltage of 3.2 V and a typical charging voltage of 3.6 V. Lithium nickel manganese cobalt (NMC) oxide cathode with graphite anodes have a 3.7 V nominal voltage with a 4.2 V max charge. The charging procedure is performed at constant voltage with current-limiting circuitry (i.e., charging with constant current until a voltage of 4.2 V is reached in the cell and continuing with a constant voltage applied until the current drops close to zero). Typically, the charge is terminated at 3% of the initial charge current. In the past, lithium-ion batteries could not be fast-charged and needed at least two hours to fully charge. Current-generation cells can be fully charged in 45 minutes or less. Some lithium-ion varieties can reach 90% in as little as 10 minutes.[61]
[edit] Charging procedure
Stage 1: Apply charging current until the voltage limit per cell is reached.[62]
Stage 2: Apply maximum voltage per cell limit until the current declines below 3% of rated charge current.[62][unreliable source?]
Stage 3: Periodically apply a top-off charge about once per 500 hours.[62][unreliable source?]
The charge time is about three to five hours, depending on the charger used. Generally, cell phone batteries can be charged at 1C and laptop-types at 0.8C, where C is the current that would discharge the battery in one hour. Charging is usually stopped when the current goes below 0.03C but it can be left indefinitely depending on desired charging time. Some fast chargers skip stage 2 and claim the battery is ready at 70% charge.[62][unreliable source?]
Top-off charging is recommended when voltage goes below 4.05 V/cell.[62][unreliable source?]
Typically, lithium-ion cells are charged with 4.2 ± 0.05 V/cell, except for military long-life cells where 3.92 V is used for extending battery life. Most protection circuits cut off if either 4.3 V or 90 °C is reached. If the voltage drops below 2.50 V per cell, the battery protection circuit may also render it unchargeable with regular charging equipment. Most battery protection circuits stop at 2.7–3.0 V per cell.[62][unreliable source?]
For safety reasons it is recommended the battery be kept at the manufacturer's stated voltage and current ratings during both charge and discharge cycles.
[edit] Variations in materials and construction
It has been suggested that Nanoball batteries be merged into this article or section. (Discuss) Proposed since September 2010.
The increasing demand for batteries has led vendors and academics to focus on improving the power density, operating temperature, safety, durability, charging time, output power, and cost of LIB solutions.
LIB types
Area
Technology
Researchers
Target application
Date
Benefit
Cathode
Manganese spinel (LMO)
Lucky Goldstar Chemical,[63] NEC, Samsung,[64] Hitachi,[65] Nissan/AESC[66]
Hybrid electric vehicle, cell phone, laptop
1996
durability, cost
Lithium iron phosphate
University of Texas/Hydro-Québec,[67]/Phostech Lithium Inc., Valence Technology, A123Systems/MIT[68][69]
Segway Personal Transporter, power tools, aviation products, automotive hybrid systems, PHEV conversions
1996
moderate density (2 A·h outputs 70 amperes) operating temperature >60 °C (140 °F)
Lithium nickel manganese cobalt (NMC)
Imara Corporation, Nissan Motor[70][71]
2008
density, output, safety
LMO/NMC
Sony, Sanyo
power, safety (although limited durability)
Lithium iron fluorophosphate
University of Waterloo[72]
2007
durability, cost (replace Li with Na or Na/Li)
Lithium air
University of Dayton Research Institute[73]
automotive
2009
density, safety[73]
5% Vanadium-doped Lithium iron phosphate olivine
Binghamton University[74]
2008
output
Anode
Lithium-titanate battery (LT)
Altairnano
automotive (Phoenix Motorcars), electrical grid (PJM Interconnection Regional Transmission Organization control area,[75] United States Department of Defense[76]), bus (Proterra[77])
2008
output, charging time, durability (20 years, 9,000 cycles), safety, operating temperature (-50–70 °C (-58–158 °F)[78][dead link]
Lithium vanadium oxide
Samsung/Subaru.[79]
automotive
2007
density (745Wh/l)[80]
Cobalt-oxide nano wires from genetically modified virus
MIT
2006
density, thickness[81]
Three-Dimensional (3D) Porous Particles Composed of Curved Two-Dimensional (2D) Nano-Sized Layers
Georgia Institute of Technology [82]
high energy batteries for electronics and electrical vehicles
2011
specific capacity > 2000 mA·h/g, high efficiency, rapid low-cost synthesis [83]
Iron-phosphate nano wires from genetically modified virus
MIT
2009
density, thickness[84][85][86]
Silicon/titanium dioxide composite nano wires from genetically modified tobacco virus
University of Maryland
explosive detection sensors, biomimetic structures, water-repellent surfaces, micro/nano scale heat pipes
2010
density, low charge time[87]
Porous silicon/carbon nanocomposite spheres
Georgia Institute of Technology
portable electronics, electrical vehicles, electrical grid
2010
high stability, high capacity, low charge time[88]
nano-sized wires on stainless steel
Stanford University
wireless sensors networks,
2007
density[89][90] (shift from anode- to cathode-limited), durability issue remains (wire cracking)
Metal hydrides
Laboratoire de Réactivité et de Chimie des Solides, General Motors
2008
density (1480 mA·h/g)[91]
Silicon Nanotubes (or Silicon Nanospheres) Confined within Rigid Carbon Outer Shells
Georgia Institute of Technology, MSE, NanoTech Yushin's group [92]
stable high energy batteries for cell phones, laptops, netbooks, radios, sensors and electrical vehicles
2010
specific capacity 2400 mA·h/g, ultra-high Coulombic Efficiency and outstanding SEI stability [93]
Electrode
LT/LMO
Ener1/Delphi,[94][95]
2006
durability, safety (limited density)
Nanostructure
Université Paul Sabatier/Université Picardie Jules Verne[96]
2006
density
[edit] Usage guidelines
[edit] Prolonging battery pack life
Depletion below the low-voltage threshold (2.4 to 2.8 V/cell, depending on chemistry) results in a dead battery which does not even appear to charge because the protection circuit (a type of electronic fuse) disables it.[97] This can be reversed in many modern batteries, especially single-cell ones, by applying a charging voltage for long enough to make the cell voltage rise above the low-voltage threshold; however this behaviour varies by manufacturer.
Lithium-ion batteries should be kept cool; they may be stored in a refrigerator.[97][98]
The rate of degradation of Lithium-ion batteries is strongly temperature-dependent; they degrade much faster if stored or used at higher temperatures.[97][99]
The rate of degradation of Lithium-ion batteries is also related to battery charge level; they degrade much faster when at 100% charge, than at lower charges. Since batteries die if deep discharged (depleted) and since a battery has some self-discharge it is frequently recommended to store batteries at 40% charge level. [100]
[edit] Multicell devices
Li-ion batteries require a Battery Management System to prevent operation outside each cell's Safe Operating Area (over-charge, under-charge, safe temperature range) and to balance cells to eliminate SOC mismatches, significantly improving battery efficiency and increasing overall capacity.[101] As the number of cells and load currents increase, the potential for mismatch also increases.[102] There are two kinds of mismatch in the pack: state-of-charge (SOC) and capacity/energy ("C/E") mismatch. Though SOC is more common, each problem limits pack capacity (mA·h) to the capacity of the weakest cell.
[edit] Safety
Lithium-ion batteries can rupture, ignite, or explode when exposed to high temperature. Short-circuiting a battery will cause the cell to overheat and possibly to catch fire. Adjacent cells may also then heat up and fail, in some cases, causing the entire battery to ignite or rupture. In the event of a fire, the device may emit dense irritating smoke.[103]
Replacing the lithium cobalt oxide cathode material in lithium-ion batteries with a lithium metal phosphate such as lithium iron phosphate, improves cycle counts, shelf life and safety, but lowers capacity. Currently, these 'safer' lithium-ion batteries are mainly used in electric cars and other large-capacity battery applications, where safety issues are critical.[104]
Lithium-ion batteries normally contain safety devices to protect the cells from disturbance. However, contaminants inside the cells can defeat these safety devices.
[edit] Recalls
In March 2007, Lenovo recalled approximately 205,000 batteries at risk of explosion. In August 2007, Nokia recalled over 46 million batteries at risk of overheating and exploding.[105] One such incident occurred in the Philippines involving a Nokia N91, which uses the BL-5C battery.[106]
In December 2006, Dell recalled approximately 22,000 laptop batteries from the U.S. market.[107] Approximately 10 million Sony batteries used in Dell, Sony, Apple, Lenovo/IBM, Panasonic, Toshiba, Hitachi, Fujitsu and Sharp laptops were recalled in 2006. The batteries were found to be susceptible to internal contamination by metal particles. Under some circumstances, these particles could pierce the separator, causing a short-circuit.[108]
In October 2004, Kyocera Wireless recalled approximately 1 million mobile phone batteries to identify counterfeits.[109]
[edit] Transport restrictions
In January 2008, the United States Department of Transportation ruled that passengers on board commercial aircraft could carry lithium batteries in their checked baggage if the batteries are installed in a device. Types of batteries affected by this rule are those containing lithium, including Li-ion, lithium polymer, and lithium cobalt oxide chemistries. Lithium-ion batteries containing more than 25 grams (0.88 oz) equivalent lithium content (ELC) are exempt from the rule and are forbidden in air travel.[110] This restriction greatly reduces the chances of the batteries short-circuiting and causing a fire.[citation needed]
Additionally, a limited number of replacement batteries may be transported in carry-on luggage. Such batteries must be sealed in their original protective packaging or in individual containers or plastic bags.[110][111]
Some postal administrations restrict air shipping (including EMS) of lithium and lithium-ion batteries, and products containing these (e.g. laptops, cell phones etc.). Among these countries and regions are Hong Kong,[112] Australia and Japan.[113]
[edit] Research
Researchers are working to improve the power density, safety, recharge cycle, cost and other characteristics of these batteries.
Solid-state designs have the potential to deliver three times the energy density of typical 2011 lithium-ion batteries at less than half the cost per kilowatt-hour. This approach eliminates binders, separators, and liquid electrolytes. By eliminating these, "you can get around 95% of the theoretical energy density of the active materials."[114]
Earlier trials of this technology ran into cost barriers, because the semiconductor industry's vacuum deposition technology cost 20–30 times too much. The new process deposits semiconductor-quality films from a solution. The nanostructured films grow directly on a substrate and then sequentially on top of each other. The process allows the firm to "spray-paint a cathode, then a separator/electrolyte, then the anode. It can be cut and stacked in various form factors."[114]
[edit] See also
Book: Lithium-ion batteries
Wikipedia Books are collections of articles that can be downloaded or ordered in print.
Potassium-ion battery
Nanowire battery
[edit] Notes
1.^ a b c d "Rechargeable Li-Ion OEM Battery Products". Panasonic.com. Retrieved 2010-04-23.
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12.^ Silberberg, M. 2006. Chemistry: The Molecular Nature of Matter and Change, 4th Ed. New York (NY): McGraw-Hill Education. p 935.
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71.^ O'Dell, John (17 December 2008). Fledgling Battery Company Says Its Technology Boosts Hybrid Battery Performance Green Car Advisor; Edmunds Inc. Retrieved 2010-06-11.
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[edit] References
Winter, M.; Brodd, J. (2004). "What Are Batteries, Fuel Cells, and Supercapacitors?" (PDF). Chemical Review 104 (104): 4245. doi:10.1021/cr020730k. Retrieved 2010-07-25.
[edit] External links
Wikimedia Commons has media related to: Lithium-ion batteries
Asahi Kasei Corporation -- Father of the lithium-ion battery
Lithium batteries at the Open Directory Project
Argonne opens chapter in battery research -- lithium air. Argonne National Labs. Press release. 14 September 2009.
Battery and Energy Technologies - Rechargeable Lithium batteries. Electropaedia; Woodbank Communications Ltd. Updated 28 April 2010.
Stanford's nanowire battery holds 10 times the charge of existing ones. Stanford Report, 18 December 2007. Press release.
The Lithium Ion Battery. E-Articles.com. (Self-publishing site).
The Future of Electric Vehicles: Setting the Record Straight on Lithium Availability. Journal of Energy Security, 27 August 2009. Keith Evans.
Researchers from Spheric Technologies and Arizona State University Describe Major Advances in the Use of Microwaves to Produce Key Lithium Ion Battery Materials; Present Papers at MS&T'10 Conference, October 17-21. Spheric Technologies. Press release. October 18, 2010.
[hide]v · d · eGalvanic cells
Non-rechargeable:
primary cells
Alkaline battery · Aluminium battery · Bunsen cell · Chromic acid cell · Clark cell · Daniell cell · Dry cell · Grove cell · Leclanché cell · Lithium battery · Mercury battery · Nickel oxyhydroxide battery · Silver-oxide battery · Weston cell · Zamboni pile · Zinc–air battery · Zinc–carbon battery · Zinc–chloride battery
Rechargeable:
secondary cells
Automotive battery · Lead–acid battery · Lead-acid battery (gel) · Lithium air battery · Lithium-ion battery · Beltway battery · Lithium-ion polymer battery · Lithium iron phosphate battery · Lithium sulfur battery · Lithium-titanate battery · Nickel-cadmium battery · Nickel hydrogen battery · Nickel-iron battery · Nickel-lithium battery · Nickel-metal hydride battery · Low self-discharge NiMH battery · Nickel-zinc battery · Potassium-ion battery · Rechargeable alkaline battery · Silicon air battery · Sodium-ion battery · Sodium-sulfur battery · Vanadium redox battery · Zinc-bromine battery · Zinc-cerium battery
Kinds of cells
Battery (including Wet cell · Dry cell) · Concentration cell · Flow battery · Fuel cell · Trough battery · Voltaic pile
Parts of cells
Anode · Catalyst · Cathode · Electrolyte · Half cell · Ions · Salt bridge · Semipermeable membrane
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They lose 20% charge capacity per year, as per wiki article.
I'm asuming this means over time the gasoline engine is used more often reducing efficiency over time.
Lithium-ion battery
From Wikipedia, the free encyclopedia
(Redirected from Li Ion)
Not to be confused with Lithium battery or Lithium-ion polymer battery.
"Lithium-ion" redirects here. For the metal element, see Lithium.
Lithium-ion battery
Nokia Li-ion battery for powering a mobile phone
specific energy
100-250 W·h/kg [1]
(0.36-0.90 MJ/kg)
energy density
250-620 W·h/L [2]
(0.90-2.23 MJ/L)
specific power
~250-~340 W/kg[1]
Charge/discharge efficiency
80-90%[3]
Energy/consumer-price
2.5 W·h/US$[4]
Self-discharge rate
8% at 21 °C
15% at 40 °C
31% at 60 °C
(per month)[5]
Cycle durability
400-1200 cycles
[6]
Nominal cell voltage
3.6 / 3.7 V
A lithium-ion battery (sometimes Li-ion battery or LIB) is a family of rechargeable battery types in which lithium ions move from the negative electrode to the positive electrode during discharge, and back when charging. Chemistry, performance, cost, and safety characteristics vary across LIB types. Unlike lithium primary batteries (which are disposable), lithium-ion electrochemical cells use an intercalated lithium compound as the electrode material instead of metallic lithium.
Lithium-ion batteries are common in consumer electronics. They are one of the most popular types of rechargeable battery for portable electronics, with one of the best energy densities, no memory effect, and a slow loss of charge when not in use. Beyond consumer electronics, LIBs are also growing in popularity for military, electric vehicle, and aerospace applications.[7] Research is yielding a stream of improvements to traditional LIB technology, focusing on energy density, durability, cost, and intrinsic safety.
Lithium-ion batteries account for 67% of all portable secondary battery sales in Japan. In the UK lithium-ion batteries account for 4.3% of all portable battery sales and in the EU 1%. [8] [9] [10]
Contents
[hide] 1 Charge and discharge
2 Construction
3 Formats
4 History
5 Electrochemistry 5.1 Positive electrodes
5.2 Negative electrodes
5.3 Electrolytes
6 Advantages and disadvantages 6.1 Advantages
6.2 Disadvantages 6.2.1 Cell life
6.2.2 Internal resistance
6.2.3 Safety requirements
7 Specifications and design
8 Charging procedure
9 Variations in materials and construction
10 Usage guidelines 10.1 Prolonging battery pack life 10.1.1 Multicell devices
10.2 Safety 10.2.1 Recalls
10.2.2 Transport restrictions
11 Research
12 See also
13 Notes
14 References
15 External links
[edit] Charge and discharge
During discharge, lithium ions Li+ carry the current from the negative to the positive electrode, through the non-aqueous electrolyte and separator diaphragm.[11]
During charging, an external electrical power source (the charging circuit) applies a higher voltage (but of the same polarity) than that produced by the battery, forcing the current to pass in the reverse direction. The lithium ions then migrate from the positive to the negative electrode, where they become embedded in the porous electrode material in a process known as intercalation.
[edit] Construction
Cylindrical 18650 cell before closing
The three primary functional components of a lithium-ion battery are the anode, cathode, and electrolyte. The anode of a conventional lithium-ion cell is made from carbon, the cathode is a metal oxide, and the electrolyte is a lithium salt in an organic solvent.[12]
The most commercially popular anode material is graphite. The cathode is generally one of three materials: a layered oxide (such as lithium cobalt oxide), a polyanion (such as lithium iron phosphate), or a spinel (such as lithium manganese oxide).[13]
The electrolyte is typically a mixture of organic carbonates such as ethylene carbonate or diethyl carbonate containing complexes of lithium ions.[14] These non-aqueous electrolytes generally use non-coordinating anion salts such as lithium hexafluorophosphate (LiPF6), lithium hexafluoroarsenate monohydrate (LiAsF6), lithium perchlorate (LiClO4), lithium tetrafluoroborate (LiBF4), and lithium triflate (LiCF3SO3).
Depending on materials choices, the voltage, capacity, life, and safety of a lithium-ion battery can change dramatically. Recently, novel architectures using nanotechnology have been employed to improve performance.
Pure lithium is very reactive. It reacts vigorously with water to form lithium hydroxide and hydrogen gas. Thus, a non-aqueous electrolyte is typically used, and a sealed container rigidly excludes water from the battery pack.
Lithium ion batteries are more expensive than NiCd batteries but operate over a wider temperature range with higher energy densities, while being smaller and lighter. They are fragile and so need a protective circuit to limit peak voltages.
[edit] Formats
Nissan Leaf's lithium-ion battery pack.
Li-ion cells are available in various formats, which can generally be divided into four groups:[15]
Small cylindrical (solid body without terminals, such as those used in laptop batteries)
Large cylindrical (solid body with large threaded terminals)
Pouch (soft, flat body, such as those used in cell phones)
Prismatic (semi-hard plastic case with large threaded terminals, often used in vehicles' traction packs)
The lack of case gives pouch cells the highest energy density; however, pouch cells (and prismatic cells) require an external means of containment to prevent expansion when their SOC level is high.[16]
[edit] History
Varta Lithium-ion battery, Museum Autovision, Altlussheim, Germany
Lithium batteries were first proposed by M.S. Whittingham at Binghamton University, at Exxon, in the 1970s.[17] Whittingham used titanium(II) sulfide as the cathode and lithium metal as the anode.
The reversible intercalation in graphite[18][19] and intercalation into cathodic oxides [20][21] was also already discovered in the 1970s by J.O. Besenhard at TU Munich. He also proposed the application as high energy density Lithium cells[22][23]
Primary lithium batteries in which the anode is made from metallic lithium pose safety issues. As a result, lithium-ion batteries were developed in which both anode and cathode are made of a material containing lithium ions.
In 1979, John Goodenough demonstrated a rechargeable cell with high cell voltage in the 4V range using lithium cobalt oxide (LiCoO2) etc. as positive electrode and Lithium metal as negative electrode.[24] This innovation provided the positive electrode material which made the lithium-ion battery (LIB) possible. LiCoO2 is a stable positive electrode material which acts as a donor of Lithium ions, which meant that it could be used with negative electrode material other than Lithium metal. By enabling the use of stable and easy-to-handle negative electrode materials, LiCoO2 opened a whole new range of possibilities for novel rechargeable battery systems.
In 1981, Bell Labs developed a workable graphite anode[25] to provide an alternative to the lithium metal battery.
In 1982, Rachid Yazami demonstrated the reversible electrochemical intercalation of Lithium in graphite.[26][27] The organic electrolytes available at the time would decompose during charging if used with graphite negative electrode, preventing the early development of a rechargeable battery which employed the Lithium/graphite system. Yazami used a solid electrolyte to demonstrate that Lithium could be reversibly intercalated in graphite through an electrochemical mechanism.
In 1983, Dr. Michael Thackeray, Goodenough, and coworkers identified manganese spinel as a cathode material.[28] Spinel showed great promise, given low-cost, good electronic and lithium ion conductivity, and three-dimensional structure which gives it good structural stability. Although pure manganese spinel fades with cycling, this can be overcome with chemical modification of the material.[29] Manganese spinel is currently used in commercial cells.[30]
In 1985, Akira Yoshino assembled a prototype cell using as anode a certain carbonaceous material into which lithium ions could be inserted and as cathode lithium cobalt oxide (LiCoO2) etc. which is stable in air.[31] By using an anode material without metallic lithium, safety was dramatically improved over batteries which used lithium metal. The use of lithium cobalt oxide (LiCoO2) enabled industrial-scale production to be achieved easily.
This was the birth of the current lithium-ion battery.
Then in 1991, Sony and Asahi Kasei released the first commercial lithium-ion battery.
In 1989, Goodenough and Arumugam Manthiram of the University of Texas at Austin showed that cathodes containing polyanions, e.g. sulfates, produce higher voltages than oxides due to the inductive effect of the polyanion.[32]
In 1996, Goodenough, Akshaya Padhi and coworkers identified lithium iron phosphate (LiFePO4) and other phospho-olivines (lithium metal phosphates with olivine structure) as cathode materials.[33]
In 2002, Yet-Ming Chiang and his group at MIT showed a substantial improvement in the performance of lithium batteries by boosting the material's conductivity by doping it with aluminum, niobium and zirconium. The exact mechanism causing the increase became the subject of a debate.[34]
In 2004, Chiang again increased performance by utilizing iron-phosphate particles of less than 100 nanometers in diameter. This decreased particle density by almost one hundredfold, increased the cathode's surface area and improved capacity and performance. Commercialization led to a competitive market and a patent infringement battle between Chiang and Goodenough.[34]
[edit] Electrochemistry
The three participants in the electrochemical reactions in a lithium-ion battery are the anode, cathode, and electrolyte.
Both the anode and cathode are materials into which, and from which, lithium can migrate. During insertion (or intercalation) lithium moves into the electrode. During the reverse process, extraction (or deintercalation), lithium moves back out. When a lithium-based cell is discharging, the lithium is extracted from the anode and inserted into the cathode. When the cell is charging, the reverse occurs.
Useful work can only be extracted if electrons flow through a closed external circuit. The following equations are in units of moles, making it possible to use the coefficient x.
The positive electrode half-reaction (with charging being forwards) is: [35]
The negative electrode half-reaction is:
The overall reaction has its limits. Overdischarge supersaturates lithium cobalt oxide, leading to the production of lithium oxide,[36] possibly by the following irreversible reaction:
Overcharge up to 5.2 Volts leads to the synthesis of cobalt(IV) oxide, as evidenced by x-ray diffraction[37]
In a lithium-ion battery the lithium ions are transported to and from the cathode or anode, with the transition metal, cobalt (Co), in LixCoO2 being oxidized from Co3+ to Co4+ during charging, and reduced from Co4+ to Co3+ during discharge.
[edit] Positive electrodes
Electrode material
Average potential difference
Specific capacity
Specific energy
LiCoO2
3.7 V
140 mA·h/g
0.518 kW·h/kg
LiMn2O4
4.0 V
100 mA·h/g
0.400 kW·h/kg
LiNiO2
3.5 V
180 mA·h/g
0.630 kW·h/kg
LiFePO4
3.3 V
150 mA·h/g
0.495 kW·h/kg
Li2FePO4F
3.6 V
115 mA·h/g
0.414 kW·h/kg
LiCo1/3Ni1/3Mn1/3O2
3.6 V
160 mA·h/g
0.576 kW·h/kg
Li(LiaNixMnyCoz)O2
4.2 V
220 mA·h/g
0.920 kW·h/kg
[edit] Negative electrodes
Electrode material
Average potential difference
Specific capacity
Specific energy
Graphite (LiC6)
0.1-0.2 V
372 mA·h/g
0.0372-0.0744 kW·h/kg
Hard Carbon (LiC6)
? V
? mA·h/g
? kW·h/kg
Titanate (Li4Ti5O12)
1-2 V
160 mA·h/g
0.16-0.32 kW·h/kg
Si (Li4.4Si)[38]
0.5-1 V
4212 mA·h/g
2.106-4.212 kW·h/kg
Ge (Li4.4Ge)[39]
0.7-1.2 V
1624 mA·h/g
1.137-1.949 kW·h/kg
[edit] Electrolytes
The cell voltages given in the Electrochemistry section are larger than the potential at which aqueous solutions can electrolyze, in addition lithium is highly reactive to water, therefore, nonaqueous or aprotic solutions are used.
Liquid electrolytes in lithium-ion batteries consist of lithium salts, such as LiPF6, LiBF4 or LiClO4 in an organic solvent, such as ethylene carbonate, dimethyl carbonate, and diethyl carbonate. A liquid electrolyte conducts lithium ions, acting as a carrier between the cathode and the anode when a battery passes an electric current through an external circuit. Typical conductivities of liquid electrolyte at room temperature (20 °C (68 °F)) are in the range of 10 mS/cm (1 S/m), increasing by approximately 30–40% at 40 °C (104 °F) and decreasing by a slightly smaller amount at 0 °C (32 °F)[40]
Unfortunately, organic solvents easily decompose on anodes during charging. However, when appropriate organic solvents are used as the electrolyte, the solvent decomposes on initial charging and forms a solid layer called the solid electrolyte interphase (SEI),[41] which is electrically insulating yet provides sufficient ionic conductivity. The interphase prevents decomposition of the electrolyte after the second charge. For example, ethylene carbonate is decomposed at a relatively high voltage, 0.7 V vs. lithium, and forms a dense and stable interface.[citation needed]
A good solution for the interface instability is the application of a new class of composite electrolytes based on POE (poly(oxyethylene)) developed by Syzdek et al.[42][43] It can be either solid (high molecular weight) and be applied in dry Li-polymer cells, or liquid (low molecular weight) and be applied in regular Li-ion cells.
Another issue that Li-ion technology is facing is safety. Large scale application of Li cells in Electric Vehicles needs a dramatic decrease in the failure rate. One of the solutions is the novel technology based on reversed-phase composite electrolytes, employing porous ceramic material filled with electrolyte.[44]
[edit] Advantages and disadvantages
Note that both advantages and disadvantages depend on the materials and design that make up the battery. This summary reflects older designs that use carbon anode, metal oxide cathodes, and lithium salt in an organic solvent for the electrolyte.
[edit] Advantages
A lithium-ion battery from a laptop computer Wide variety of shapes and sizes efficiently fitting the devices they power.
Much lighter than other energy-equivalent secondary batteries.[45]
High open circuit voltage in comparison to aqueous batteries (such as lead acid, nickel-metal hydride and nickel-cadmium).[46] This is beneficial because it increases the amount of power that can be transferred at a lower current.
No memory effect.
Self-discharge rate of approximately 5-10% per month, compared to over 30% per month in common nickel metal hydride batteries, approximately 1.25% per month for Low Self-Discharge NiMH batteries and 10% per month in nickel-cadmium batteries.[47] According to one manufacturer, lithium-ion cells (and, accordingly, "dumb" lithium-ion batteries) do not have any self-discharge in the usual meaning of this word.[35] What looks like a self-discharge in these batteries is a permanent loss of capacity (see Disadvantages). On the other hand, "smart" lithium-ion batteries do self-discharge, due to the drain of the built-in voltage monitoring circuit.
Components are environmentally safe as there is no free lithium metal.[citation needed]
[edit] Disadvantages
[edit] Cell life
Charging forms deposits inside the electrolyte that inhibit ion transport. Over time, the cell's capacity diminishes. The increase in internal resistance reduces the cell's ability to deliver current. This problem is more pronounced in high-current applications. The decrease means that older batteries do not charge as much as new ones (charging time required decreases proportionally).
High charge levels and elevated temperatures (whether from charging or ambient air) hasten capacity loss.[48][49] Charging heat is caused by the carbon anode (typically replaced with lithium titanate which drastically reduces damage from charging, including expansion and other factors).[50]
A Standard (Cobalt) Li-ion cell that is full most of the time at 25 °C (77 °F) irreversibly loses approximately 20% capacity per year. Poor ventilation may increase temperatures, further shortening battery life. Loss rates vary by temperature: 6% loss at 0 °C (32 °F), 20% at 25 °C (77 °F), and 35% at 40 °C (104 °F). When stored at 40%–60% charge level, the capacity loss is reduced to 2%, 4%, and 15%, respectively.[51][citation needed] In contrast, the calendar life of LiFePO4 cells is not affected by being kept at a high state of charge.[52]
[edit] Internal resistance
The internal resistance of standard (Cobalt) lithium-ion batteries is high compared to both other rechargeable chemistries such as nickel-metal hydride and nickel-cadmium, and LiFePO4 and lithium-polymer cells.[53] Internal resistance increases with both cycling and age.[49][54][55] Rising internal resistance causes the voltage at the terminals to drop under load, which reduces the maximum current draw. Eventually increasing resistance means that the battery can no longer operate for an adequate period.
To power larger devices, such as electric cars, connecting many small batteries in a parallel circuit is more effective[56] and efficient than connecting a single large battery.[57]
[edit] Safety requirements
If overheated or overcharged, Li-ion batteries may suffer thermal runaway and cell rupture.[58] In extreme cases this can lead to combustion. Deep discharge may short-circuit the cell, in which case recharging would be unsafe.[59] To reduce these risks, Lithium-ion battery packs contain fail-safe circuitry that shuts down the battery when its voltage is outside the safe range of 3–4.2 V per cell.[35][47] When stored for long periods the small current draw of the protection circuitry itself may drain the battery below its shut down voltage; normal chargers are then ineffective. Many types of lithium-ion cell cannot be charged safely below 0°C.[60]
Other safety features are required in each cell:[35]
shut-down separator (for overtemperature)
tear-away tab (for internal pressure)
vent (pressure relief)
thermal interrupt (overcurrent/overcharging)
These devices occupy useful space inside the cells, add additional points of failure and irreversibly disable the cell when activated. They are required because the anode produces heat during use, while the cathode may produce oxygen. These devices and improved electrode designs reduce/eliminate the risk of fire or explosion.
These safety features increase costs compared to nickel metal hydride batteries, which require only a hydrogen/oxygen recombination device (preventing damage due to mild overcharging) and a back-up pressure valve.[47]
[edit] Specifications and design
Specific energy density: 150 to 250 W·h/kg (540 to 900 kJ/kg)[1]
Volumetric energy density: 250 to 620 W·h/l (900 to 1900 J/cm³)[2]
Specific power density: 300 to 1500 W/kg (@ 20 seconds and 285 W·h/l)[1]
Because lithium-ion batteries can have a variety of cathode and anode materials, the energy density and voltage vary accordingly.
Lithium-ion batteries with a lithium iron phosphate cathode and graphite anode have a nominal open-circuit voltage of 3.2 V and a typical charging voltage of 3.6 V. Lithium nickel manganese cobalt (NMC) oxide cathode with graphite anodes have a 3.7 V nominal voltage with a 4.2 V max charge. The charging procedure is performed at constant voltage with current-limiting circuitry (i.e., charging with constant current until a voltage of 4.2 V is reached in the cell and continuing with a constant voltage applied until the current drops close to zero). Typically, the charge is terminated at 3% of the initial charge current. In the past, lithium-ion batteries could not be fast-charged and needed at least two hours to fully charge. Current-generation cells can be fully charged in 45 minutes or less. Some lithium-ion varieties can reach 90% in as little as 10 minutes.[61]
[edit] Charging procedure
Stage 1: Apply charging current until the voltage limit per cell is reached.[62]
Stage 2: Apply maximum voltage per cell limit until the current declines below 3% of rated charge current.[62][unreliable source?]
Stage 3: Periodically apply a top-off charge about once per 500 hours.[62][unreliable source?]
The charge time is about three to five hours, depending on the charger used. Generally, cell phone batteries can be charged at 1C and laptop-types at 0.8C, where C is the current that would discharge the battery in one hour. Charging is usually stopped when the current goes below 0.03C but it can be left indefinitely depending on desired charging time. Some fast chargers skip stage 2 and claim the battery is ready at 70% charge.[62][unreliable source?]
Top-off charging is recommended when voltage goes below 4.05 V/cell.[62][unreliable source?]
Typically, lithium-ion cells are charged with 4.2 ± 0.05 V/cell, except for military long-life cells where 3.92 V is used for extending battery life. Most protection circuits cut off if either 4.3 V or 90 °C is reached. If the voltage drops below 2.50 V per cell, the battery protection circuit may also render it unchargeable with regular charging equipment. Most battery protection circuits stop at 2.7–3.0 V per cell.[62][unreliable source?]
For safety reasons it is recommended the battery be kept at the manufacturer's stated voltage and current ratings during both charge and discharge cycles.
[edit] Variations in materials and construction
It has been suggested that Nanoball batteries be merged into this article or section. (Discuss) Proposed since September 2010.
The increasing demand for batteries has led vendors and academics to focus on improving the power density, operating temperature, safety, durability, charging time, output power, and cost of LIB solutions.
LIB types
Area
Technology
Researchers
Target application
Date
Benefit
Cathode
Manganese spinel (LMO)
Lucky Goldstar Chemical,[63] NEC, Samsung,[64] Hitachi,[65] Nissan/AESC[66]
Hybrid electric vehicle, cell phone, laptop
1996
durability, cost
Lithium iron phosphate
University of Texas/Hydro-Québec,[67]/Phostech Lithium Inc., Valence Technology, A123Systems/MIT[68][69]
Segway Personal Transporter, power tools, aviation products, automotive hybrid systems, PHEV conversions
1996
moderate density (2 A·h outputs 70 amperes) operating temperature >60 °C (140 °F)
Lithium nickel manganese cobalt (NMC)
Imara Corporation, Nissan Motor[70][71]
2008
density, output, safety
LMO/NMC
Sony, Sanyo
power, safety (although limited durability)
Lithium iron fluorophosphate
University of Waterloo[72]
2007
durability, cost (replace Li with Na or Na/Li)
Lithium air
University of Dayton Research Institute[73]
automotive
2009
density, safety[73]
5% Vanadium-doped Lithium iron phosphate olivine
Binghamton University[74]
2008
output
Anode
Lithium-titanate battery (LT)
Altairnano
automotive (Phoenix Motorcars), electrical grid (PJM Interconnection Regional Transmission Organization control area,[75] United States Department of Defense[76]), bus (Proterra[77])
2008
output, charging time, durability (20 years, 9,000 cycles), safety, operating temperature (-50–70 °C (-58–158 °F)[78][dead link]
Lithium vanadium oxide
Samsung/Subaru.[79]
automotive
2007
density (745Wh/l)[80]
Cobalt-oxide nano wires from genetically modified virus
MIT
2006
density, thickness[81]
Three-Dimensional (3D) Porous Particles Composed of Curved Two-Dimensional (2D) Nano-Sized Layers
Georgia Institute of Technology [82]
high energy batteries for electronics and electrical vehicles
2011
specific capacity > 2000 mA·h/g, high efficiency, rapid low-cost synthesis [83]
Iron-phosphate nano wires from genetically modified virus
MIT
2009
density, thickness[84][85][86]
Silicon/titanium dioxide composite nano wires from genetically modified tobacco virus
University of Maryland
explosive detection sensors, biomimetic structures, water-repellent surfaces, micro/nano scale heat pipes
2010
density, low charge time[87]
Porous silicon/carbon nanocomposite spheres
Georgia Institute of Technology
portable electronics, electrical vehicles, electrical grid
2010
high stability, high capacity, low charge time[88]
nano-sized wires on stainless steel
Stanford University
wireless sensors networks,
2007
density[89][90] (shift from anode- to cathode-limited), durability issue remains (wire cracking)
Metal hydrides
Laboratoire de Réactivité et de Chimie des Solides, General Motors
2008
density (1480 mA·h/g)[91]
Silicon Nanotubes (or Silicon Nanospheres) Confined within Rigid Carbon Outer Shells
Georgia Institute of Technology, MSE, NanoTech Yushin's group [92]
stable high energy batteries for cell phones, laptops, netbooks, radios, sensors and electrical vehicles
2010
specific capacity 2400 mA·h/g, ultra-high Coulombic Efficiency and outstanding SEI stability [93]
Electrode
LT/LMO
Ener1/Delphi,[94][95]
2006
durability, safety (limited density)
Nanostructure
Université Paul Sabatier/Université Picardie Jules Verne[96]
2006
density
[edit] Usage guidelines
[edit] Prolonging battery pack life
Depletion below the low-voltage threshold (2.4 to 2.8 V/cell, depending on chemistry) results in a dead battery which does not even appear to charge because the protection circuit (a type of electronic fuse) disables it.[97] This can be reversed in many modern batteries, especially single-cell ones, by applying a charging voltage for long enough to make the cell voltage rise above the low-voltage threshold; however this behaviour varies by manufacturer.
Lithium-ion batteries should be kept cool; they may be stored in a refrigerator.[97][98]
The rate of degradation of Lithium-ion batteries is strongly temperature-dependent; they degrade much faster if stored or used at higher temperatures.[97][99]
The rate of degradation of Lithium-ion batteries is also related to battery charge level; they degrade much faster when at 100% charge, than at lower charges. Since batteries die if deep discharged (depleted) and since a battery has some self-discharge it is frequently recommended to store batteries at 40% charge level. [100]
[edit] Multicell devices
Li-ion batteries require a Battery Management System to prevent operation outside each cell's Safe Operating Area (over-charge, under-charge, safe temperature range) and to balance cells to eliminate SOC mismatches, significantly improving battery efficiency and increasing overall capacity.[101] As the number of cells and load currents increase, the potential for mismatch also increases.[102] There are two kinds of mismatch in the pack: state-of-charge (SOC) and capacity/energy ("C/E") mismatch. Though SOC is more common, each problem limits pack capacity (mA·h) to the capacity of the weakest cell.
[edit] Safety
Lithium-ion batteries can rupture, ignite, or explode when exposed to high temperature. Short-circuiting a battery will cause the cell to overheat and possibly to catch fire. Adjacent cells may also then heat up and fail, in some cases, causing the entire battery to ignite or rupture. In the event of a fire, the device may emit dense irritating smoke.[103]
Replacing the lithium cobalt oxide cathode material in lithium-ion batteries with a lithium metal phosphate such as lithium iron phosphate, improves cycle counts, shelf life and safety, but lowers capacity. Currently, these 'safer' lithium-ion batteries are mainly used in electric cars and other large-capacity battery applications, where safety issues are critical.[104]
Lithium-ion batteries normally contain safety devices to protect the cells from disturbance. However, contaminants inside the cells can defeat these safety devices.
[edit] Recalls
In March 2007, Lenovo recalled approximately 205,000 batteries at risk of explosion. In August 2007, Nokia recalled over 46 million batteries at risk of overheating and exploding.[105] One such incident occurred in the Philippines involving a Nokia N91, which uses the BL-5C battery.[106]
In December 2006, Dell recalled approximately 22,000 laptop batteries from the U.S. market.[107] Approximately 10 million Sony batteries used in Dell, Sony, Apple, Lenovo/IBM, Panasonic, Toshiba, Hitachi, Fujitsu and Sharp laptops were recalled in 2006. The batteries were found to be susceptible to internal contamination by metal particles. Under some circumstances, these particles could pierce the separator, causing a short-circuit.[108]
In October 2004, Kyocera Wireless recalled approximately 1 million mobile phone batteries to identify counterfeits.[109]
[edit] Transport restrictions
In January 2008, the United States Department of Transportation ruled that passengers on board commercial aircraft could carry lithium batteries in their checked baggage if the batteries are installed in a device. Types of batteries affected by this rule are those containing lithium, including Li-ion, lithium polymer, and lithium cobalt oxide chemistries. Lithium-ion batteries containing more than 25 grams (0.88 oz) equivalent lithium content (ELC) are exempt from the rule and are forbidden in air travel.[110] This restriction greatly reduces the chances of the batteries short-circuiting and causing a fire.[citation needed]
Additionally, a limited number of replacement batteries may be transported in carry-on luggage. Such batteries must be sealed in their original protective packaging or in individual containers or plastic bags.[110][111]
Some postal administrations restrict air shipping (including EMS) of lithium and lithium-ion batteries, and products containing these (e.g. laptops, cell phones etc.). Among these countries and regions are Hong Kong,[112] Australia and Japan.[113]
[edit] Research
Researchers are working to improve the power density, safety, recharge cycle, cost and other characteristics of these batteries.
Solid-state designs have the potential to deliver three times the energy density of typical 2011 lithium-ion batteries at less than half the cost per kilowatt-hour. This approach eliminates binders, separators, and liquid electrolytes. By eliminating these, "you can get around 95% of the theoretical energy density of the active materials."[114]
Earlier trials of this technology ran into cost barriers, because the semiconductor industry's vacuum deposition technology cost 20–30 times too much. The new process deposits semiconductor-quality films from a solution. The nanostructured films grow directly on a substrate and then sequentially on top of each other. The process allows the firm to "spray-paint a cathode, then a separator/electrolyte, then the anode. It can be cut and stacked in various form factors."[114]
[edit] See also
Book: Lithium-ion batteries
Wikipedia Books are collections of articles that can be downloaded or ordered in print.
Potassium-ion battery
Nanowire battery
[edit] Notes
1.^ a b c d "Rechargeable Li-Ion OEM Battery Products". Panasonic.com. Retrieved 2010-04-23.
2.^ a b "Panasonic Develops New Higher-Capacity 18650 Li-Ion Cells; Application of Silicon-based Alloy in Anode". greencarcongress.com. Retrieved 2011-01-31.
3.^ Valøen & Shoesmith (2007). The effect of PHEV and HEV duty cycles on battery and battery pack performance (PDF). 2007 Plug-in Highway Electric Vehicle Conference: Proceedings. Retrieved 2010-06-11.
4.^ 11.10V,6600Mah, Li-Ion, Replacement Laptop Battery For Dell (etc). Amazon.com Online Store. Retrieved 2010-06-11.
5.^ H. Abea, T. Muraia and K. Zaghibb (1999). Vapor-grown carbon fiber anode for cylindrical lithium ion rechargeable batteries. Journal of Power Sources 77:2, February 1999, pp. 110-115. DOI:10.1016/S0378-7753(98)00158-X. Retrieved 2010-06-11.
6.^ Battery Types and Characteristics for HEV ThermoAnalytics, Inc., 2007. Retrieved 2010-06-11.
7.^ Ballon, Massie Santos (14 October 2008). "Electrovaya, Tata Motors to make electric Indica". cleantech.com. Cleantech Group. Retrieved 2010-06-11.
8.^ [1] Monthly battery sales statistics - MoETI - March 2011
9.^ [2] Battery Waste Management - 2006 DEFRA
10.^ [3] EPBA statistics - 2000
11.^ David Linden, Thomas B. Reddy (ed). Handbook Of Batteries 3rd Edition. McGraw-Hill, New York, 2002 ISBN 0-07-135978-8 chapter 35
12.^ Silberberg, M. 2006. Chemistry: The Molecular Nature of Matter and Change, 4th Ed. New York (NY): McGraw-Hill Education. p 935.
13.^ Thackeray, Thomas, and Whittingham (March 2000). Science and Applications of Mixed Conductors for Lithium Batteries. mrs.com; Materials Research Society. Retrieved 2010-06-11.
14.^ MSDS: National Power Corp Lithium Ion Batteries (PDF). tek.com; Tektronix Inc., 7 May 2004. Retrieved 2010-06-11.
15.^ Battery Management Systems for Large Lithium-Ion Battery Packs page 2
16.^ Battery Management Systems for Large Lithium-Ion Battery Packs page 234
17.^ M Stanley Whittingham. Electrical Energy Storage and Intercalation Chemistry Science: 192 (4244): 1126
18.^ J.O.Besenhard and H.P. Fritz, Cathodic Reduction of Graphite in Organic Solutions of Alkali and NR 4+ Salts, J. Electroanal. Chem., 53, 329 (1974)
19.^ J.O. Besenhard, The Electrochemical Preparation and Properties of Ionic Alkali Metal and NR 4+ Graphite Intercalation Compounds in Organic Electrolytes, Carbon, 14, 111 (1976)
20.^ R. Schallhorn, R. Kuhlmann, and J.O. Besenhard, Topotactic Redox Reactions and Ion Exchange of Layered MoO3 Bronzes,, Mat. Res. Bull., 11, 83 (1976)
21.^ J.O. Besenhard and R. Schallhorn, The Discharge Reaction Mechanism of the MoO3 Electrode in Organic Electrolytes” J. Power Sources, 1, 267 (1976/77)
22.^ J.O. Besenhard and G. Eichinger, High Energy Density Lithium Cells. Part I. Electrolytes and Anodes, J. Electroanal. Chem., 68, 1 (1976); and G. Eichinger
23.^ J.O. Besenhard, High Energy Density Lithium Cells. Part II. Cathodes and Complete Cells, J. Electroanal. Chem., 72, 1 (1976)
24.^ USPTO search for inventions by "Goodenough, John"
25.^ US 4304825, Basu; Samar, "Rechargeable battery", issued 8 December 1981, assigned to Bell Telephone Laboratories
26.^ International Meeting on Lithium Batteries, Rome, April 27–29, 1982, C.L.U.P. Ed. Milan, Abstract #23
27.^ Journal of Power Sources (April–May 1983), 9 (3–4), 365–371
28.^ M.M. Thackeray, W.I.F. David, P.G. Bruce, and J.B. Goodenough (4 February 1983). "Lithium insertion into manganese spinels". Materials Research Bulletin (Elsevier) 18 (4): 461–472. doi:10.1016/0025-5408(83)90138-1.
29.^ Gholamabbas Nazri, Gianfranco Pistoia (2004). Lithium batteries: science and ... - Google Books. Springer. ISBN 9781402076282. Retrieved 2009-10-08.
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[edit] References
Winter, M.; Brodd, J. (2004). "What Are Batteries, Fuel Cells, and Supercapacitors?" (PDF). Chemical Review 104 (104): 4245. doi:10.1021/cr020730k. Retrieved 2010-07-25.
[edit] External links
Wikimedia Commons has media related to: Lithium-ion batteries
Asahi Kasei Corporation -- Father of the lithium-ion battery
Lithium batteries at the Open Directory Project
Argonne opens chapter in battery research -- lithium air. Argonne National Labs. Press release. 14 September 2009.
Battery and Energy Technologies - Rechargeable Lithium batteries. Electropaedia; Woodbank Communications Ltd. Updated 28 April 2010.
Stanford's nanowire battery holds 10 times the charge of existing ones. Stanford Report, 18 December 2007. Press release.
The Lithium Ion Battery. E-Articles.com. (Self-publishing site).
The Future of Electric Vehicles: Setting the Record Straight on Lithium Availability. Journal of Energy Security, 27 August 2009. Keith Evans.
Researchers from Spheric Technologies and Arizona State University Describe Major Advances in the Use of Microwaves to Produce Key Lithium Ion Battery Materials; Present Papers at MS&T'10 Conference, October 17-21. Spheric Technologies. Press release. October 18, 2010.
[hide]v · d · eGalvanic cells
Non-rechargeable:
primary cells
Alkaline battery · Aluminium battery · Bunsen cell · Chromic acid cell · Clark cell · Daniell cell · Dry cell · Grove cell · Leclanché cell · Lithium battery · Mercury battery · Nickel oxyhydroxide battery · Silver-oxide battery · Weston cell · Zamboni pile · Zinc–air battery · Zinc–carbon battery · Zinc–chloride battery
Rechargeable:
secondary cells
Automotive battery · Lead–acid battery · Lead-acid battery (gel) · Lithium air battery · Lithium-ion battery · Beltway battery · Lithium-ion polymer battery · Lithium iron phosphate battery · Lithium sulfur battery · Lithium-titanate battery · Nickel-cadmium battery · Nickel hydrogen battery · Nickel-iron battery · Nickel-lithium battery · Nickel-metal hydride battery · Low self-discharge NiMH battery · Nickel-zinc battery · Potassium-ion battery · Rechargeable alkaline battery · Silicon air battery · Sodium-ion battery · Sodium-sulfur battery · Vanadium redox battery · Zinc-bromine battery · Zinc-cerium battery
Kinds of cells
Battery (including Wet cell · Dry cell) · Concentration cell · Flow battery · Fuel cell · Trough battery · Voltaic pile
Parts of cells
Anode · Catalyst · Cathode · Electrolyte · Half cell · Ions · Salt bridge · Semipermeable membrane
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Categories: Lithium-ion batteries | Rechargeable batteries | Metal-ion batteries | Product recalls | Product safety scandals
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Disclaimers
27 weeks ago
The right thing??The carbon footprint for electric vehicles is larger than for gasoline fired vehicles.
20k to replace the battery at 8 yrs. Contiual voltage depletion over time. After 6 yrs the vehicle will have zero value.
ijv5x
19 weeks ago
We almost always get 300,000 miles to our hondas, doges, and mazdas we've had. Then take them to the junk yard to get $1000 dollars.
14 weeks ago
I have a 95 Honda Civic ( which I love love love) has 189,000 and have never had an issue with anything. I am in the market for a used hybrid now, but am nervous about getting stuck with one that will soon need a battery replacement. Battery advice anyone? :) Is it enevitable that all hybrid vehicles will eventually need new batteries, or does this only happen because the vehicle is poorly cared for?
9 weeks ago
Riley.You mention that your IMA light is on but wont that cause you check engine light to come on ? and wont that cause you to fail your inspection. I also have a IMA light on @ 175400 and it wont pass inspection in NY. It seem to run great but I wont be able to drive it any longer without spending big bucks to get it repaired. Any suggerstions ouy there.
Paul from western NY
5 weeks ago
The question remains: Does the inevitable decline in battery performance over time reduce the gas economy compared the Corolla or Civic. That plus the initial price differential might make the hybrid an uneconomical choice and, perhaps, not a clear cut "green" choice.
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