Category Archives: Automotive

Why the Boeing Dreamliner’s batteries burst into flames

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Boeing’s Dreamliner is currently grounded due to two of their Li-Ion batteries having burst into flames, one in flight, and another on the ground. Two accidents of the same type in a small fleet is no little matter as an airplane fire can be deadly on the ground or at 50,000 feet.

The fires are particularly bad on the Dreamliner because these lithium batteries control virtually everything that goes on aboard the plane. Even without a fire, when they go out so does virtually every control and sensor. So why did they burn and what has Boeing done to take care of it? The simple reason for the fires is that management chose to use Li-Cobalt oxide batteries, the same Li-battery design that every laptop computer maker had already rejected ten years earlier when laptops using them started busting into flames. This is the battery design that caused Dell and HP to recall every computer with it. Boeing decided that they should use a massive version to control everything on their flagship airplane because it has the highest energy density see graphic below. They figured that operational management would insure safety even without the need to install any cooling or sufficient shielding.

All lithium batteries have a negative electrode (anode) that is mostly lithium. The usual chemistry is lithium metal in a graphite matrix. Lithium metal is light and readily gives off electrons; the graphite makes is somewhat less reactive. The positive electrode (cathode) is typically an oxide of some sort, and here there are options. Most current cell-phone and laptop batteries use some version of manganese nickel oxide as the anode. Lithium atoms in the anode give off electrons, become lithium ions and then travel across to the oxide making a mixed ion oxide that absorbs the electron. The process provides about 4 volts of energy differential per electron transferred. With cobalt oxide, the cathode reaction is more or less CoO2 + Li+ + e– —> LiCoO2. Sorry to say this chemistry is very unstable; the oxide itself is unstable, more unstable than MnNi or iron oxide, especially when it is fully charged, and especially when it is warm (40 degrees or warmer) 2CoO2 –> Co2O3 +1/2O2. Boeing’s safety idea was to control the charge rate in a way that overheating was not supposed to occur.

Despite the controls, it didn’t work for the two Boeing batteries that burst into flames. Perhaps it would have helped to add cooling to reduce the temperature — that’s what’s done in lap-tops and plug-in automobiles — but even with cooling the batteries might have self-destructed due to local heating effects. These batteries were massive, and there is plenty of room for one spot to get hotter than the rest; this seems to have happened in both fires, either as a cause or result. Once the cobalt oxide gets hot and oxygen is released a lithium-oxygen fire can spread to the whole battery, even if the majority is held at a low temperature. If local heating were the cause, no amount of external cooling would have helped.

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Something that would have helped was a polymer interlayer separator to keep the unstable cobalt oxide from fueling the fire; there was none. Another option is to use a more-stable cathode like iron phosphate or lithium manganese nickel. As shown in the graphic above, these stable oxides do not have the high power density of Li-cobalt oxide. When the unstable cobalt oxide decomposed there was oxygen, lithium, and heat in one space and none of the fire extinguishers on the planes could put out the fires.

The solution that Boeing has proposed and that Washington is reviewing is to leave the batteries unchanged, but to shield them in a massive titanium shield with the vapors formed on burning vented outside the airplane. The claim is that this shield will protect the passengers from the fire, if not from the loss of electricity. This does not appear to be the best solution. Airbus had planned to use the same batteries on their newest planes, but has now gone retro and plans to use Ni-Cad batteries. I don’t think that’s the best solution either. Better options, I think, are nickel metal hydride or the very stable Lithium Iron Phosphate batteries that Segway uses. Better yet would be to use fuel cells, an option that appears to be better than even the best batteries. Fuel cells are what the navy uses on submarines and what NASA uses in space. They are both more energy dense and safer than batteries. As a disclaimer, REB Research makes hydrogen generators and purifiers that are used with fuel-cell power.

More on the chemistry of Boeing’s batteries and their problems can be found on Wikipedia. You can also read an interview with the head of Tesla motors regarding his suggestions and offer of help.

 

A visit to the Buxbaum laboratory from Metromedia

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It’s a slow news day in Detroit, so the folks from Metromedia came to visit my laboratory at REB Research. You can visit too. We’re doing cool stuff most of the time, we’re working on a hydrogen-fueled plane that stays aloft for weeks (not that cool, actually, the Hindenberg did it in the 30s). On this particular day I’ve got a cool hat on, and a beige suit. I’m putting hydrogen in my car. Hydrogen increases the speed of combustion, and so it adds to milage — or it has when we’ve added it from electrolysis sources.buxbaum-003

The fun thing about science is that there are always surprises.

Adding hydrogen to a Malibu at REB Research

Adding hydrogen to a Malibu at REB Research

Purifying the Hydrogen from Browns gas, HHO, etc.

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Perhaps the simplest way to make hydrogen is to stick two electrodes into water and to apply electricity. The gas that is produced is mostly hydrogen, and is sometimes suitable for welding or for addition to an automobile engine to increase the mileage. Depending on the electrodes and whether salt is added to the water, the gas that is produced can be Browns gas, HHO,  town gas, or some relative of the three. We are sometimes asked if we can purify the product of this electrolysis, and my answer is typically: “maybe,” or “it depends.”

If the electrode was made of stainless steel and the water contained only KOH or baking soda, the gas that results will be mostly hydrogen and you will be able to purify it somewhat with a polymer membrane if you wish. The gas isn’t very explosive generally, since most of the oxygen that results from the electrolysis will go into rusting out the electrodes. The reaction is thus, H2O + Fe –> H2 + FeO. To see if this is what you’ve got, you can use determine the ratio of gas production with a simple version of the Hoffman apparatus made from (for example) two overturned glass jars, or by separating the electrodes with a paper towel. You can also determine the H2 to O2 ratio (if you know a bit more physics) from a measure of the amperage and the rate of gas production. The hydrogen you form with steel plates will always contain some oxygen though, as well as some nitrogen and water vapor. While a polymer membrane will remove most of the oxygen and nitrogen in this gas, it won’t remove all, and it will not generally remove any of the water. With this gas, I suspect that you would be better off just using it as it is. This is particularly so if the fraction of oxygen is more than a few percent: hydrogen with more oxygen than this becomes quite explosive.

Since this gas will contain water, you probably don’t want to store it, and you probably don’t want to purify it over a metal, either, There are two reasons for this: the water can condense out during storage, and will tend to rust whatever metal it contacts (it’s often alkaline). What’s more, the small amount of oxygen in the hydrogen is likely to react over a hydrogen storage metal to form water and heat. This may give rise to the explosion you were trying to avoid. This is clearly the quick a dirty approach to making hydrogen.

Another version of electrolysis gas, one that’s even quicker and dirtier than the above involves the use of table salt instead of KOH or baking soda. The hydrogen that results will contain chlorine as an impurity, and will be quite toxic, but it will be somewhat less explosive.The hydrogen will smell like bleach and the water you use will turn slightly greenish and quite alkaline. Both the liquid and gas are definitely bad news unless your aim was to make chlorine and alkali; this is called the chlor-alkali process for a reason. On a personal note, as a 12 year old I tried this and was confused about why I got equal volumes of gas on the cathode and anode. The reason was that I was making Cl2, and not O2: the chemistry is 2 H2O + 2 NaCl –> H2 + Cl2 + 2 NaOH. I then I used the bromide version reaction to make a nice sample of bromine liquid. That is, I used KBr instead of table salt. Bromine is brown, oily, and only sparingly soluble in water.

Another version of this electrolysis process involves the use of graphite electrodes. If you are lucky, this will give you a mix of CO and hydrogen and not H2 and O2. This mix is a called “town gas.” It’s a very good welding gas since it is not explosive. It is, however, quite toxic. If you begin to get a headache using this gas stop immediately: you’re experiencing CO poisoning. The reaction here is H2O + C –> H2 + CO. CO headaches just get worse and worse until you die. If you are not lucky here you can get HHO instead of town gas, and this is quite explosive: H2O –> H2 + 1/2 O2. The volume ratio will be a key clue as to which you are making; another clue is to put a small volume in a paper bag and light it. If the bag explodes with a terrific bang, you’ve made the wrong gas. Stop!

With all of these gases I would recommend that you add a polymer of paper membrane in the water between the electrodes. Filter paper will work fine for this as will ceramic paper; the classic membrane for this was asbestos. If you keep the two product gas streams separate as soon as they are formed, you’ll avoid most of your explosion-safety issues. Few people take this advice, I’ve found; they think there must be some simpler way. Trust me: this is the classic, safe way to make electrolysis hydrogen.

A balloon filled with pure hydrogen will not ignite. To show you, here is a 2.5 min long video where I poke a lit cigar into a mylar balloon filled with hydrogen from my membrane reactor generators. Note that this hydrogen does not even burn in the balloon because it is oxygen free. As a safety check try this with your hydrogen, but only on a much-smaller scale. Pure hydrogen will not go boom, impure hydrogen will. My advice: keep safe and healthy. You’ll feel better that way, and your heirs will be less inclined to sue me.

In case you are wondering how electrolysis hydrogen can add to the gas mileage, the simple answer is that it increases the combustion speed and the water vapor decreases the parasitic loss due to vacuum. I’ve got some more information on this here. I hope this advice helps with your car project or any other electrolysis option. In my opinion, one should use a membrane in the water to separate the components at formation in all but the smallest experiments and with the smallest amperage sources. Even these should be done only in a well-ventilated room or on a car that is parked outside of the house. Many of the great chemists of the 1800s died doing experiments like these; learn from their mistakes and stay among the living.

How hydrogen and/or water can improve automobile mileage (mpg)

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In case you’ve ever wondered why it was that performance cars got such poor milage, or why you got such bad milage in the city, the biggest single problem has to do with the vacuum drawn by the engine, some of the problem has to do with the speed of combustion, some has to do with rolling friction, and some with start/stop loss too. Only a very small fraction of the energy is lost on air friction until you reach highway speeds.

Lets consider vacuum loss first as it is likely the worst offender. A typical US car, e.g. a Chevy Malibu, has a 3.5 liter engine (a performance car has an engine that’s much larger). As you toodle down a street at 35 mph, your engine is going at about 2000 rpm, or 33 rps. Since the power required to move the car is far less than the 200 hp that the car could deliver, the air intake is throttled so that the engine is sucking a vacuum of about 75 kpa (10 psi for those using English units). To calculate the power loss this entails, multiply 33*3.5*80; this is about 8662 Watts, or 12 hp. To find the energy use per mile, divide by your average speed, 25 mph (it would be 35 mph, but you sometimes stop for lights). 8 kW/25 mph = .21 kW-hr/mile. One finds, as I’ll show that the car expends more energy sucking this vacuum than pushing the car itself. This is where the majority of the city mpg goes in a normal car, but it’s worse in a high performance car is worse since the engine is bigger. In city driving, the performance mpg will be lower than for a Malibu even if the performance car is lighter, if it has better aerodynamics (it does), and if you never stop at lights.

The two other big places were city mileage goes is overcoming rolling friction and the need to stop and go at lights, stop signs, etc. The energy used for rolling friction is the force it would take to push your car on level ground when in neutral times the distance. For a typical car, the push force is about 70 lbs or 32 kgs or 315 Nt; it’s roughly proportional to the car’s weight. At 35 mph, or 15.5 m/s, the amount of power this absorbs is calculated as the product of force and speed: 15.5*315 = 4882 W, or about 6.5 hp. The energy use is 4.9 kW/35 mph =.14 kWhr/mile. The energy loss from stop lights is similar to this, about .16 kWhr/mile, something you can tell by getting the car up to speed and seeing how far it goes before it stops. It’ll go about 2-3 blocks, a little less distance than you are likely to go without having to stop. Air resistance adds a very small amount at these speeds, about 2000 W, 2.7 hp, or .05 kWhr/mile; it’s far more relevant at 65 mph, but still isn’t that large.

If you add all this together, you find the average car uses about .56 kWhr/mile. For an average density gasoline of 5.6 lb/gal, and average energy-dense gasoline, 18,000 BTU/lb, and an average car engine efficiency of 11000 BTU/kWhr, you can now predict an average city gas mileage of 16.9 mpg, about what you find experimentally. Applying the same methods to highway traffic at 65 mph, you predict .38 kWhr/mile, or 25 mpg. Your rpms are the same on the highway as in the city, but the throttle is open so you get more power and loose less to vacuum.

Now, how do you increase a car’s mpg. If you’re a Detroit automaker you could reduce the weight of the car, or you the customer can clean the junk out of your trunk. Every 35 lbs or so increases the rolling friction by about 1%. These is another way to reduce rolling friction and that’s to get low resistance tires, or keep the tires you’ve got full of air. Still, what you’d really like to do is reduce the loss to vacuum energy, since vacuum loss is a bigger drain on mpg.

The first, simple way to reduce vacuum energy loss is to run lean: that is, to add more air than necessary for combustion. Sorry to say, that’s illegal now, but in the olden days before pollution control you could boost your mpg by adjusting your carburator to add about 10% excess of air. This reduced your passing power and the air pollution folks made it illegal (and difficult) after they noticed that it excess air increased NOx emissions. The oxygen sensor on most cars keeps you from playing with the carburator these days.

Another approach is to use a much smaller engine. The Japanese and Koreans used to do this, and they got good milage as a result. The problem here is that you now had to have a very light car or you’d get very low power and low acceleration — and no American likes that. A recent approach to make up for some of the loss of acceleration is by adding a battery and an electric motor; you’re now making a hybrid car. But the batteries add significant cost, weight and complexity to these cars, and not everyone feels this is worth it. So now on to my main topic: adding steam or hydrogen.

There is plenty of excess heat on the car manifold. A simile use of this heat is to warm some water to the point where the vapor pressure is, for example, 50 kPa. The pressure from this water adds to the power of your engine by allowing a reduction in the vacuum to 50 kPa or less. This cuts the vacuum loss at low speeds. At high speed and power the car automatically increases the air pressure and the water stops evaporating, so there is no loss of power. I’m currently testing this modification on my own automobile partly for the fun of it, and partly as a preface to my next step: using the car engine heat to run the reaction CH3OH + H2O –> CO2 + H2. I’ll talk more about our efforts adding hydrogen elsewhere, but thought you might be interested in these fundamentals.

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Hydrogen addition to an automobile engine

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Today, I began a series of experiments putting hydrogen into my car engine. Hydrogen is a combustion promotor, increasing the flame speed significantly, even at low compositions, and it has a very high octane value, so it does not cause pre-ignition. I used my Chevy Malibu, shown, and generated the hydrogen using one of our (REB Research’s) methanol-reformer hydrogen generators. I used a small hydrogen generator we sell for gas chromatographic use, and put 280 ccm hydrogen into engine, as shown. This is enough to provide 1% of the energy content about during idle.

I’ve not measured mpg change yet (as a stationary experiment the mpg is 0), but was really looking for outward signs of knock or other engine problems. Adding 280 ccm of hydrogen should increase the flame speed by ~2%, which should increase the degree of high pressure combustion, and this should increase the mpg by about 3% or 4% if you don’t include the hydrogen energy. So far, I saw no ill effects: no ill sounds and no check engine lights.

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Hydrogen added to a Chevy Malibu engine at REB Research

About half the hydrogen energy comes from waste heat of the engine, and half the methanol. Either way this energy is very cheap: methanol costs about $1.20/gal, about half of what gasoline does on a per-energy basis.  Next step is to make my hydrogen generator mobile, and check the effect on mpg. I’m glad it worked OK so far. There was a reporter watching.