Tag Archives: lithium

Exercise helps fight depression, lithium helps too.

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With the sun setting earlier, and the threat of new COVID lockdowns, there is a real threat of a depression, seasonal and isolation. A partial remedy is exercise; it helps fight depression whether you take other measures not. An article published last month in the Journal of Affective Disorders reviewed 22 studies of the efficacy of exercise, particularly as an add-on to drugs and therapy. Almost every study showed that exercise helped, and in some studies it helped a lot. See table below. All of the authors are from the University of British Columbia. You can read the article here.

From “Efficacy of exercise combined with standard treatment for depression compared to standard treatment alone: A systematic review and meta-analysis of randomized controlled trials.” by JacquelineLee1 et al.In virtually every study, exercise helps fight depression.

For those who are willing to exercise, there are benefits aside from mental health. Even a daily walk around the block helps with bone strength, weight control, heart disease, plus the above mentioned improvement in mood. More exercise does more. If you bicycle without a helmet, you’re likely to live longer than if you drive.

For those who can’t stand exercise, or if exercise isn’t quite enough to send away the blues, you can try therapy, medication, and/or diet. There is some evidence that food that are high in lithium help fight depression. These food include nuts, beans, tomatoes, some mineral waters, e.g. from Lithia springs, GA. The does is about 1/100 the dose given as a bipolar treatment, but there is evidence that even such small doses help. Lithium was one of the seven ingredients in seven up — it was the one that was supposed to cheer you up. See some research here.

Robert Buxbaum, October 7, 2021.

Keeping your car batteries alive.

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Lithium-battery cost and performance has improved so much that no one uses Ni-Cad or metal hydride batteries any more. These are the choice for tools, phones, and computers, while lead acid batteries are used for car starting and emergency lights. I thought I’d write about the care and trade-offs of these two remaining options.

As things currently stand, you can buy a 12 V, lead-acid car battery with 40 Amp-h capacity for about $95. This suggests a cost of about $200/ kWh. The price rises to $400/kWh if you only discharge half way (good practice). This is cheaper than the per-power cost of lithium batteries, about $500/ kWh or $1000/ kWh if you only discharge half-way (good practice), but people pick lithium because (1) it’s lighter, and (2) it’s generally longer lasting. Lithium generally lasts about 2000 half-discharge cycles vs 500 for lead-acid.

On the basis of cost per cycle, lead acid batteries would have been replaced completely except that they are more tolerant of cold and heat, and they easily output the 400-800 Amps needed to start a car. Lithium batteries have problems at these currents, especially when it’s hot or cold. Lithium batteries deteriorate fast in the heat too (over 40°C, 105°F), and you can not charge a lithium car battery at more than 3-4 Amps at temperatures below about 0°C, 32°F. At higher currents, a coat of lithium metal forms on the anode. This lithium can react with water: 2Li + H2O –> Li2O + H2, or it can form dendrites that puncture the cell separators leading to fire and explosion. If you charge a lead acid battery too fast some hydrogen can form, but that’s much less of a problem. If you are worried about hydrogen, we sell hydrogen getters and catalysts that remove it. Here’s a description of the mechanisms.

The best thing you can do to keep a lead-acid battery alive is to keep it near-fully charged. This can be done by taking long drives, by idling the car (warming it up), or by use of an external trickle charger. I recommend a trickle charger in the winter because it’s non-polluting. A lead-acid battery that’s kept at near full charge will give you enough charge for 3000 to 5000 starts. If you let the battery completely discharge, you get only 50 or so deep cycles or 1000 starts. But beware: full discharge can creep up on you. A new car battery will hold 40 Ampere-hours of current, or 65,000 Ampere-seconds if you half discharge. Starting the car will take 5 seconds of 600 Amps, using 3000 Amp-s or about 5% of the battery’s juice. The battery will recharge as you drive, but not that fast. You’ll have to drive for at least 500 seconds (8 minutes) to recharge from the energy used in starting. But in the winter it is common that your drive will be shorter, and that a lot of your alternator power will be sent to the defrosters, lights, and seat heaters. As a result, your lead-acid battery will not totally charge, even on a 10 minute drive. With every week of short trips, the battery will drain a little, and sooner or later, you’ll find your battery is dead. Beware and recharge, ideally before 50% discharge

A little chemistry will help explain why full discharging is bad for battery life (for a different version see Wikipedia). For the first half discharge of a lead-acid battery, the reaction Is:

Pb + 2PbO2 + 2H2SO4  –> PbSO4 + Pb2O2SO4 + 2H2O.

This reaction involves 2 electrons and has a -∆G° of >394 kJ, suggesting a reversible voltage more than 2.04 V per cell with voltage decreasing as H2SO4 is used up. Any discharge forms PbSO4 on the positive plate (the lead anode) and converts lead oxide on the cathode (the negative plate) to Pb2O2SO4. Discharging to more than 50% involves this reaction converting the Pb2O2SO4 on the cathode to PbSO4.

Pb + Pb2O2SO4 + 2H2SO4  –> 2PbSO4 + 2H2O.

This also involves two electrons, but -∆G < 394 kJ, and voltage is less than 2.04 V. Not only is the voltage less, the maximum current is less. As it happens Pb2O2SO4 is amorphous, adherent, and conductive, while PbSO4 is crystalline, not that adherent, and not-so conductive. Operating at more than 50% results in less voltage, increased internal resistance, decreased H2SO4 concentrations, and lead sulfate flaking off the electrode. Even letting a battery sit at low voltage contributes to PbSO4 flaking off. If the weather is cold enough, the low concentration H2SO4 freezes and the battery case cracks. My advice: Get out your battery charger and top up your battery. Don’t worry about overcharging; your battery charger will sense when the charge is complete. A lead-acid battery operated at near full charge, between 67 and 100% will provide 1500 cycles, about as many as lithium. 

Trickle charging my wife's car. Good for battery life. At 6 Amps, expect this to take 3-6 hours.

Trickle charging my wife’s car: good for battery life. At 6 Amps, expect a full charge to take 6 hours or more. You might want to recharge the battery in your emergency lights too. 

Lithium batteries are the choice for tools and electric vehicles, but the chemistry is different. For longest life with lithium batteries, they should not be charged fully. If you change fully they deteriorate and self-discharge, especially when warm (100°F, 40°C). If you operate at 20°C between 75% and 25% charge, a lithium-ion battery will last 2000 cycles; at 100% to 0%, expect only 200 cycles or so.

Tesla cars use lithium batteries of a special type, lithium cobalt. Such batteries have been known to explode, but and Tesla adds sophisticated electronics and cooling systems to prevent this. The Chevy Volt and Bolt use lithium batteries too, but they are less energy-dense. In either case, assuming $1000/kWh and a 2000 cycle life, the battery cost of an EV is about 50¢/kWh-cycle. Add to this the cost of electricity, 15¢/kWh including the over-potential needed to charge, and I find a total cost of operation of 65¢/kWh. EVs get about 3 miles per kWh, suggesting an energy cost of about 22¢/mile. By comparison, a 23 mpg car that uses gasoline at $2.80 / gal, the energy cost is 12¢/mile, about half that of the EVs. For now, I stick to gasoline for normal driving, and for long trips, suggest buses, trains, and flying.

Robert Buxbaum, January 4, 2018.

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.

battery-materials-energy-densities-battery-university

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.