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Prospects for Lithium-ion Batteries in Automotive Applications from AABC Week

17 May 2007

Enthusiasm—and especially expectations—for lithium-ion battery technology applied to hybrids, plug-in hybrids and electric vehicles is demonstrably growing, fueled by the convergence of very substantive technical advances and the clear need to make rapid progress to reduce the consumption of fossil fuels in transportation.

This year’s Advanced Automotive Battery Conference (AABC) and related Symposia, being held this week in Long Beach, California, are enjoying the largest attendance ever. Yet with the enthusiasm comes caution. There are still technical issues to be resolved for automotive applications.  At a high level the outstanding issues can be categorized as safety and cost; at a cell level the issues come down to the selection of electrolytes, electrode materials, separators, and design.

Dr. Menahem Anderman, the President of Advanced Automotive Batteries and the organizer of the conferences, projects that lithium-ion battery sales may capture 5% of the hybrid and electric vehicle market by 2010, 17% by 2012 and 36% by 2015.  While NiMH batteries would still dominate that market segment, clearly their marketshare would be beginning to decline. A corollary forecast is that plug-in hybrids—assuming that lithium-ion chemistries are required for those applications—are unlikely to reach commercial volumes (more than 20,000 units per year) by 2015.

There are several non-technical wildcards that could accelerate the rate of growth in the adoption of lithium-ion technology. A rapid spike in petroleum costs and/or concern over global warming that translates into government mandates for fuel efficiency would have a major impact. There are also wildcards that could slow the rate of growth. A reduction in oil prices, steady adoption of diesels in the US market, the failure of advanced HEV, PHEV or EV batteries to provide at least 8 years of life in most applications, and the inability of the HEV industry to reduce system costs at the steady rate now projected, could each slow the pace of adoption.

Lithium-ion battery chemistry is attractive because it offers higher power and energy (1.3 to 1.7 times) than that of current NiMH technology. That higher power and energy should result in a lower number of cells being required in the pack (lowering cost); lower heat generation (if impedance is suppressed); a higher usable SOC (state-of-charge) range (yet to be proven); a lower metal cost per kWh (especially for certain cathode candidates); and potentially a lower long-term overall cost.

Electrolytes. There are three basic pathways to a thermal event with a lithium-ion battery: an internal short circuit (which is uncontrollable, outside of trying to ensure that it doesn’t happen through manufacturing quality), an external short circuit, and an overcharge situation.

Researchers at Ube Industries explored whether or not a tailored electrolyte could reduce the flammability of a battery in a failure condition (field or abuse). They found that while a non-flammable solvent could reduce the flammability issue, it also deteriorated battery performance.

Dr. Khalil Amine from Argonne National Laboratory described efforts in improving li-ion battery life using advanced salt and electrolyte additives. Argonne has found that maganese-spinel systems, combined with an alternative salt, could provide excellent calendar life, outstanding safety and low cost. Such a battery could meet the FreedomCar requirements ands could be the most suitable for HEV applications.

Argonne has found that the use of electrolyte additives can stabilize the battery, and reduce heat flow. An advanced Li1+x(Ni1/3CO1/3MN1/3)1-xO2 system offers high power and relatively low cost. This could be improved with the addition of a new electrolyte additive: LiC2O4BF2.

Air Products, probably better known for its industrial gases, presented the results of its work with an electrolyte salt family: the StabiliLife salts. The Li2B12FxH12-x slats provided better cell thermal stability than LiPF6 systems.

Chemetall GmbH described its work with lithium bis(oxalato) borate, known as LiBOB, for enhanced safety and stability.

Cathode materials. The selection of a cathode (the positive electrode) material is one of the areas in which battery makers are striving to differentiate themselves. There are four main candidates for cathode materials, plus blends:

  • LiNiCoAlO2: The most proven, but the most thermally unstable at high states of charge.

  • LiNiCoMnO2: This material is gaining momentum, although there is not much durability data yet.

  • LiMn2O4: Life at elevated temperatures has not yet been solved.

  • LiFePO4: The most thermally stable, but with lower voltage and lower energy. Modified iron phosphate cathodes are the choice of A123Systems and Valence. Saft, one of the well-established large-format li-ion battery companies, uses a Phostech iron phosphate as its cathode material. (Phostech is the licensor of the standard lithium iron phosphate material developed by Dr. Goodenough at the University of Texas.)

  • Blends of different materials, hopefully making the whole greater than the sum of the parts, according to Dr. Anderman.

HPL, a spin-off from Dr. Michael Grätzel’s “Laboratoire de photonique et interfaces” at the Ecole Polytechnique Federale de Lausanne (EPFL), Switzerland, described its work with lithium manganese phosphate as a new high-voltage li-ion cathode. The LiMnPO4 material offers durability, safe performance and cost effectiveness, according to HPL.

There are four phosphates from which to choose for a cathode material: iron, cobalt, nickel and  manganese. According to HPL, manganese is essentially a voltage compromise between the other three, and a nanostructured manganese phosphate can offer high rate performance, yet be safe and durable. HPL noted that Toyota has been working with the manganese cathode material.

In addition to iron phosphates, Valence is looking at vanadium-based oxides as attractive materials when coupled with a phosphate group.

Safety. Safety is a critical issue for an emerging enabling technology such as lithium-ion batteries. As J.B. Stroubel, the CTO for Tesla Motors, noted during his presentation, it doesn't matter how many gasoline fires that cars suffer annually; because electric and hybrid technology both are relatively new, any such event would have a disproportionate impact.

While the prospects of such hazardous events remain relatively high, there is a great deal of work underway to mitigate the hazard risks. USABC, for example, is working on quantifying risk with a hazard risk number, and using that approach as a mechanism to drive mitigating responses from manufacturers.

Safety issues fall into two primary categories: events resulting from abuse, and events resulting from field failure.

Field failure—a safety-related event that occurs during the normal operation of a device resulting from a manufacturing problem—must be made less severe as well as less frequent. The recent spate of battery failures in laptops and the resulting recalls in laptops were field failures.

In their presentation, Tiax argued that new approaches to safety are required, including recognition of the processes associated with field failure as a research area.

The safety “cloud” and other uncertainties in the lithium-ion market will not stop the growth of that market for HEVs, said Dr. Anderman, it will just make its growth slow—slower than many would like to see.

And in that context, he said, “It is smart of the car companies to go slow.”

May 17, 2007 in Batteries | Permalink | Comments (25) | TrackBack (0)

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The comment, "It is smart of the car companies to go slow", by the president of AAB,is a telling comment. Everyone chastises the major automakers for dragging their feet, when in reality, there must be safety/performance/durablity/cost issues to be fully met before offering. Not partially met, but fully met.

Automakers will be taking a chance with offerings that could jeapordize their whole public perception. The startup Zaps and Teslas of this world need not worry about such perceptions. They are not well know like a Ford or GM, and as such, can change their name to something else if they suffer a major brand name thrashing, due to the result of a flawed offering.

And yes I see our future personal transportation is in electrics, and there is room for both the GMs and Teslas of this world to move forward and deliver as they are able. The Jay Lenos and George Clooneys of this world may help spawn vehicles for the everyday common man, by buying these Teslas etc. I am optimistic about a better tomorrow.

"It is smart of the car companies to go slow"

Except that Toyota and Honda went forward with NiMH batteries in their hybrids back in 1997, long before the costs of the batteries were anywhere near low enough to allow a profit and before the longevity of NiMH in hybrids in real-world use had even been established.

Now both Toyota and Honda are the market leaders in hybrids with a headstart that the others will find difficult to catch up with. "Going slow" was not what gave them this advantage.

There are lots of safety issues. Everyone wants everything yesterday, but when an HEV bursts into flames due to an internal battery short, everyone says that you should have been more careful. Haste makes waste is an old saying and one that can apply to engineering development when it comes to millions of cars and lives.

http://www.valence.com/SafetyVideo.asp

http://www.a123systems.com/html/tech/safety.html

To put into words what Clett is saying by pointing to the Valence and A123systems sites:

The AAB, this article, and the comments all are focused on an issue that is (technically speaking, though not in terms of PR) behind us already. The remaining issues of cost and superior design will both be solved as fast as the marketplace allows.

One word NANOSAFE.

One word NANOSAFE.

One word NANOSAFE.

One word NANOSAFE.

One word NANOSAFE.

There are three promising battery technologies in play:
Pd, NiMH, and LiIon: The new carbon anode Pb battery from Firefly shows promise as an interim solution because it is safe enough and can be ramped up to mass production swiftly; The NiMH battery patents are under control of the oil companies through Cobasys, so it's not going anywhere soon unless Chevron/Texaco has a change of heart and right now it appears their concentration is to support diesel ICEs; LiIon appears to be the future solution when it is safe enough for wide spread auto usage.

So why not design and build gasoline/ethanol autos as plug-in hybrids, for long range use, and pure BEVs for short range? Both with battery modules that are exchangeable as the technology advances.

The use of diesel does nothing but perpetuate the continuation of the dirty, inefficient ICE and associated even more expensive emissions controls.

Toyota's Masatami Takimoto says the new Prius lithium-ion batteries are ready right now.

http://www.greencarcongress.com/2007/05/reports_toyotas.html#more

I doubt they would skimp on safety, performance or cost.

When it comes to saving fuel, everyone talks about hybrid and electric. Wile, there are other technologies like the integrated starter generator (ISG) and electro magnetic valve (EMV) control that can be applied to currect 100 million of cars that are already on the road. These two combined can save upto 20% fuel usage.

BMW have done that with their new 1-series in Europe.

Hope, they offer that as a aftermarket conversion soon.

Anytime you concentrate large amounts of power in a small space the potential for disaster exists.
Will there be problems mastering this new method? Of course there will.
The first time some shade-tree mechanic starts poking around with a screwdriver in a Lithium Ion battery pack, we will hear about how dangerous they are.
Careless activities around gasoline have killed lots of people also.
There already exists an untapped body of knowledge about LI use; Computers, PDAs, cell-phones, model cars, boats and airplanes.

Lucas-

There's a video on youtube of a safety test that was done with A123 cells versus conventional lithium ion:

http://www.youtube.com/watch?v=A9ayuFBDrSg

The conventional lithium ion battery exploded. The A123 battery did essentially nothing.

As was stated previously, the safety issues are becoming more and more a thing of the past.

I have some doubts wheather we should change from ic-engines and Hybrids to only electric cars as long as we only change the drive train.
The good thing will be improved air quality in city centres. But I am very concerned about a all out fall out in the production of electricity for all these e-cars in 10 or 15 years time. Now and in the next years we burn the fuel and pass the exhaust gases through a system to clean them up.
But what is about the standard power plants now and in 10, 15 years ahead in use?
How about fumes there?
Next problem will be the consumer. Now everyone is familiar what 30mpg and 110HP means. But how about KW and KWh? Does any housewife know what her refrigerater draws out of the grid?
What I see ahead are many 500KW cars "plus", that will consumate lots of energy.

To safe energy and increase air pollution need more revolutionary steps than just going from ic- to e-driven cars.

Michel: The beauty of moving from ICE to electric is that we go from consuming an energy source in the vehicle to using an energy carrier. The electricity you will use can come from any source. Hopefully we will use the cleanest possible. But even the dirtiest sources of energy are easiest to control in stationary generating facilities. As for the consumer, they'll get used to it. I live in Canada where we switched from imperial measurement to metric. It takes a while but you get used to it. As for muscle cars... we'll never get rid of them. At least they won't be so bloody loud.

Michel,
A "muscle car" with 500kw of power still can be very energy efficient, since the electric motor is the most efficient at low load. As load increases, efficiency will decrease somewhat. This is in contrast to gasoline engine which has poor efficiency at light loads, hence sport cars with oversized engines have lower efficiency in comparison to other cars of the same size. The high cost of battery and power inverter will discourage the use of BEV in large-size SUV's.

Overall, from well to wheel, no other method of propulsion can beat electricity in term of efficiency. Even as dirty as coal, clean coal technology can be used to eliminate exhaust stack pollution as the result of using coal for electricity, that is, if we are serious about pollution control. It would be more economical to clean up power plants rather than the exhaust pipe of each car.

The article seems very negative. A small market share by 2015?

One of the problems is the lack of focus on BEVs and PHEVs in Europe. PHEVs are actually not far off from being economically advantageous for buyers given the cost of fuel in Europe.

Perhaps a company to watch is Renault - a number of Renaults are being adapted by Cleanova / Dassault and due for release around 2008.

Maybe quick charge stations could work if done properly. You slow charge over night and get a respectable range and if you need more you can stop at a quick charge station.

The only thing left is long trips and that is why I favor dual fuel hybrids.
Electric for around town, CNG for commutes and gasoline/ethanol for trips.

The situation is very simple : as long as battery prices remain above a certain level, then series hybrids like the VOLT will be the practical way to go and will accomplish probably 98% of the good effects of all-electrics at a fraction of the cost. All-electrics,
as should be obvious to practically anyone still breathing, are not yet practical vehicles. Nor, at this time, is there any infrastructure, even for that small segment that could make use of fast charge stations.
Despite the fast recharge capabilities of some, they are still just as range bound as the EV-1 was.
The Tesla is a joke that has no significance - it's another well-publicized effort by publicity seeking over-the-hill Hollywood types like Gooney Clooney and his unreliable buddy Ed Begley. They'd accomplish more with a bottle of hair dye.

Once again, humanity prepares to throw itself with lemming-like abandon into a new fad with no thought to the consequences and sustainability of its actions.

Yes, the Lithium God must now be worshipped by all and woe to the Unbelievers who dare to protest: "Excuse me, but where is the Lithium going to come from when supply can't keep up with demand today from 100% pa laptop/ mobile phone growth in Asia? Chile? Pinochet Mark 2? Bolivia? Argentina? China? What's the price going to be when production has to increase by a factor of 10 or more? Yes of course, let's trade the western hating Arabs for Gringo hating Latinos - who have even more reason to dislike US interventionism. Excellent - sound decision making, the basis of US foreign policy since King George was given the shove. Or was he?"

NASA's requirements for the mars pathfinders and the planned manned flight to mars has produced research designed to power that solar energy requires as a forward process.
Heavy duty research funded by NASA and passed along in grants to U.S. Hi- Tech Corporations and their
partnerships with engineering graduate schools like Rutgers and Georgia Tech among others, have produced hyper-powered lithium devices that will power the manned expedition to mars.

In time these lithium innovations will be advanced to the degree of powering passenger vehicles. There is allot more to this and Mars will be for immediate future the extent of this new electric power.

Do not underestimate the power in the new formulas that are partially available on materials science engineering sites. The future of clean air autos reaches beyond the hydro carbon approaches.

For more misinformation on this NASA will be the source. Political posturing by the last two administrations have forced NASA to pull in their horns on this.

A careful reading of doping certain chemicals will shed a degree of the potential of the standard view of lithium power possibilities.

Check the patent applications and see what the future holds.

The Reporter

What is the procedure to prepare sodium iron phosphate .

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