If your cat has nine lives, shouldn't your battery have at least two?

Let’s see if you can answer this pop quiz: How much capacity fade can you tolerate in your battery before you consider it “dead”?

The answer (as usual) depends on the application.

If you have a laptop and it is anything like mine, then “dead” is when you get 10 mins of run time and you decide to bite the bullet and get a new battery. With some laptops (the one that comes to mind is made by a company whose name starts with a D and ends with a L and has four letters) getting one year from your battery is considered very good.

But laptop batteries are $50. And most customers are probably going to go back and get their next laptop based on price anyway, so there is no long-term effect of giving someone a bad battery. And if your laptop battery dies you can use it plugged in (i.e., as a desktop).

But if you had an EV which run’s 200 miles and if in, say, 3 years you start to get 160 miles, you can be confident that you will sitting in the dealership demanding that they change the battery for you. At $10-$30k a pop you are not about to pay for another battery.

And running your car with a long cord connected to an outlet can be a bit problematic.

But, as definitions go, most manufacturers will consider a battery to be at the end-of-life if it has lost 20-25% of its capacity. In some applications (e.g., HEVs) 20% loss of power is considered end-of-life. The less expensive the battery, the higher the loss that is tolerated and vice versa.

What this means is that when your EV battery is considered dead, it still has 80% of its capacity left.

Despite the fact that you are reading this blog, I’m going to go out on a limb here and assume that you are a smart person. Right about now, you must be thinking to yourself that it is stupid to call something dead when there is 80% of it left.

Do you get new brakes or tires when they have depleted by 20%?

No! You wait till your tires are bald and you skid into your auto repair shop and stop the car by crashing into something soft.

By now you are, hopefully, having this epiphany that there may be a hidden business idea here. One that involves taking these “dead” EV/PHEV batteries and using it someplace else.

Maybe ship it to some other country where they may not be as picky about the number of miles you can get?

Or maybe if you can find an application where energy density were not important, you can repurpose these batteries to sell it for these applications.

While you chew on that, let me change subjects.

Did you know that as states like California decide to enact renewable standards, utilities companies are going to have a problem? California promises that by 2020, 33% of the state’s electricity will come from renewable sources. So let’s say that to satisfy the mandate, the utilities decide to build a giant solar farm in the middle-of-nowhere (Tracy?). But even in the middle-of-nowhere the sun does not shine at night.

So enter storage as the savior. You charge the battery during the day and discharge it to power the cities at night. Transmission allowed us to space-shift the electricity (generate in point A, use it at Point B); storage allows us to time-shift. Its the DVR (or TiVo) of the grid.

And how much electricity are we talking about storing? California uses electricity in the range of giga watt hours (GWh). So a lot!

Some of you may have heard of AB2514. Its a legislation in the state of California that requires utilities to incorporate storage in the grid. The utilities will need to store 2.25% of the daytime peak power by 2014 and 5% by 2020. This is probably the first explicit mandate calling for storage to be a part of the grid.

For all you veteran battery folks who thought the community did not know how to lobby, take heart. We may be nowhere close to what the hydrogen guys have done, but it is a start!

But let’s back to the storage issue.

So storage is the DVR of the grid. And because your DVR is not moving, it can be big (and ugly if it is like my DVR).

But DVRs cost extra money and they die every few years. Batteries are a lot more like your DVR than you can imagine!

Meaning, the energy density of the battery is not that important for this application. The great thing about middle-of-nowhere is that there is a lot of it out there. What is important, however, is the cost.

Hence the interest in taking “used” vehicle batteries and using it in grid applications. A second life, if you will.

Think of the possibilities: If your battery lasts say 15 years instead of 7 years, then you just doubled the time to amortize the upfront cost. You can ask the utilities to buy the car batteries and lease it to the consumer. Once the battery is “dead”, the utility moves it to grid applications and starts its second life. The consumer does not have to worry about paying $15,000 extra for the battery or worry about it dying on them. Someone else owns it; all I need to worry about is making sure I don’t get into a crash and ruin my warranty.

There are other themes on this business plan, but you get the idea.

All this is sounding so great that I’m contemplating sending an email to my bosses telling them what I really think about my job.

But wait a second. This whole blog survives only because we hate our energy storage devices. How many examples can we think of for our batteries lasted more than a few years? My car battery, which died after 7 years, has been the only battery that has done me proud. And I was lucky to get anything close to that!

We all spend an inordinate amount of time babying our batteries and asking how we can extend the life, and here I’m claiming that we can get a second life from our batteries. There must be a reason why my post “pull the plug, your battery will thank you” has the highest hit among all the posts.

What exactly are we missing?

Turns out that we are not missing anything. The second life concept is being pushed by business-types. For a biz. dev. guy this makes perfect sense. But the real question is: Does this make sense for the tech guy in the back actually doing the testing?

Let’s look at this in detail.

If you plot the capacity of a battery versus cycle number you will see that different batteries fade differently. Some batteries fade rapidly in the 1st few cycles and then the capacity stabilizes. Others increase in capacity in the 1st few cycles then level off and then starts a linear fade.

And in some batteries, as you keep cycling them there is a point where the curve starts to “roll over”. In other words, what began as a linear fade starts to accelerate. When this occurs, you are a few cycles away from a complete dead battery (i.e., you can’t even power your watch with it!).

Lets talk a bit more technical for a minute. Those not interested, move a few paragraphs over.

Let's take a Li-ion batteries with a NCM cathode with 14% 1st cycle irreversible loss and a graphite anode with 8% 1st cycle loss. After formation, the battery discharge is dictated by the voltage of the cathode when the battery reaching the cutoff voltage. There is still lithium in the anode. Think of this as an anode-discharge buffer.

But then let us assume that the cathode works very well. The anode, as anodes tend to do, still has a small side reaction because the SEI (which is a passive layer on the anode expected to protect it) is not quite as protecting as we hoped for.

As each cycle proceeds, the lithium comes out of the cathode and a small part goes into making a new SEI and does not intercalate into the anode. As you discharge, you start to slowly deplete this anode buffer. Each cycle slowly pushes the anode potential higher and higher. At some point, all the buffer is fully depleted.

Before this buffer was depleted, if you looked at the graph of capacity vs cycle number you would not have seen any capacity fade. When you hit this point, you will start to see the fade and what you observe is like a roll over. The slope of the capacity fade curve changed.

In some cases, this change starts to accelerate the fade because of the placement of the cutoff potential in the battery.

Ergo... battery fade is nonlinear and just because you have a particular kind of fade in the first five hundred cycles does not mean the fade can be predicted over the next five hundred cycles.

All right, so you think the battery you are making is different. It has a cathode that has less irreversible loss compared to the cathode. So you don’t have the same chemical problem.

But maybe you have a mechanical degradation problem.

All batteries “breath” as they charge and discharge. As each cycle proceeds, you are slowly swinging the volume of the battery. The whole electrode is under stress (compressive in one direction and tensile on the other). Fatigue starts to set in. After repeated cycling, at some point cracking and breaking start to become a problem. Now we have a definite capacity fade.

As some of the particles break and stop participating in the reaction, the rest of the particles have to take the load and these particles are stressed further and this accelerates their fade.

And these effects depend on the kind of cycling that has been conducted. A 3 hour discharge (like that in a EV) will have a different fade characteristic compared to a 1/2 hour discharge (like in a 10 mile PHEV).

Let us try a third case. Let’s say you have a battery pack consisting of 100’s of cells (or 8000 cells if you are at Tesla). Now, its kind of hard to make all the batteries exactly the same. When you manufacture batteries the yield is not that great and companies typically wait three to four weeks before binning (sorting) the batteries. But batteries are not binned for consistent life, because there is no way to do that. Instead they are binned for self-discharge, which does not tell us much about the life.

So let’s say that as the pack is cycled, you start having a few cells fading at a faster rate. Then the cells that are good are going to work that much harder and so they will start to fade more. This will also result in an acceleration of the fade. And because its not possible to predict a priori at what rate each cells will be fading, its impossible to predict how long the whole pack will last.

If that sounded complicated it was a desperate attempt to hide my insecurities by trying to convince you that I know something about batteries.

The short summary: Battery fade is complicated and difficult to predict.

Now, not all batteries are going to do this. Some battery chemistries are better than others. And some companies (that can make consistent cells) will be better than others. But the question remains: How do we predict what is going to happen in 15 years, when the weather report seems so far off for the next day?

But why predict. Why not just cycle these batteries; wait for them to die; and use this data to find out how to cost the battery and amortize it; and then sit back and watch the moolah pile up.

Because it takes.... 15 years to get this information and we don’t have another 15 years for this business plan to come into effect. To be fair, we have been testing these batteries for a few years now and have some data. But this is nowhere close to the number of years of data needed and so we still can’t say for sure how many more cycles/years the batteries will last.

So why not do accelerated testing, you ask? Because one is not sure if the method used to accelerate the fade (e.g. increasing the temperature) results in the different fade mechanism becoming dominant. Chemistry has this nasty habit of being hard!

So all the biz dev types have a problem: If you can’t predict how many cycles/years the battery will last how do you price the batteries today?

And the tech guy in the back of the room doing all the testing is sweating because he/she knows the complexity and knows that it is hard to predict how the battery is going to behave so far in the future.

Personally I think the concept is great and in time we will know how to make this a profitable business plan.

But for now, I’m not going to send that email to my bosses. I’m thinking about buying a house and I need the paycheck!

Venkat

This week in sulfation

First off, I have to apologize to all 7 of my regular readers for not making a post in a while. I have been busy and hence the hiatus. Between watching reruns of Curb your Enthusiasm, election ads, and the Giants world series games, I need more time in a day. But all good things have to come to an end. I hope to resume regular postings starting now.

This week, I was rudely reminded that just because you know how batteries work does not mean that you can deal with a battery problem. But first some background.

Subaru's are excellent cars and I would highly recommend buying one. They are well made, they run great, and they hardly give you any problems (touch wood). But Subaru's also have small quirks that can be bewildering and a bit infuriating. Like not having a remote trunk opener or having only 3 wiper speeds. Or having this one light that does not turn off when the ignition is off and is so hidden that you can't tell that its on in the first place.

The light serves no real purpose, except to make sure to keep the battery industry thriving. Long story short, "someone" left that light on on Sunday (and I'm not saying who).

A bit more background: My car is 7 years old. My battery is (or was as of yesterday, but I'm getting ahead of myself) the original battery.

Monday morning at 7 AM I get to my car to start driving to San Francisco Intl. to catch a flight to Washington DC to be at the center of the action during election day (Tuesday). I was using a meeting on energy storage for grid applications (think storing solar and wind electricity) as an excuse to get someone else to pay for the trip. I was going to be gone all week.

Except my grand plan was crumbling because my car appeared to have a dead battery. I quickly realized what had happened.

When professionals are thrown into a crisis, they do not think, they react. Think Jason Bourne coming across an assassin or Neo coming across Agent Smith (in the Matrix).

Just so there is no confusion: I consider myself to be a professional.

In a matter of seconds the pieces started to fall into place in my brain without any real thinking. I knew my battery was probably pretty sulfated (and corroded with lots of shedding, for that matter). I opened the hood, took one look at the battery and I could literally see the sulfation on the plates (through the grime that covered the hard polypropylene battery shell). I knew that if I jumped the car right away I had a chance of saving the battery. I also knew that if I left it in the discharged state all week, I would probably sulfate it more and maybe end up killing the battery altogether.

To remind you, when you discharge a lead-acid battery you form lead sulfate. Lead sulfate is pretty insulating. But it has a bit of solubility in the electrolyte (sulfuric acid). This leads to some Pb2+ ions in solution. When you charge, these Pb2+ ions allow you to get back to the charged compound. As you react the Pb2+, more lead sulfate dissolves.

Sulfation is a process by which the lead sulfate starts to agglomerate together to form large crystals. This leads to a loss of surface area. What this means is that you don't have enough area for the electrolyte to dissolve the lead sulfate to form Pb2+. So charging the battery gets harder. Sulfation takes a while; maybe in the order or days. Not hours.

Sulfation is reversible. But you have to charge the battery very very (very) slowly so that you slowly dissolve the large crystals of lead sulfate to Pb2+ and convert them back to the charged state. But, who has the patience to wait all week to charge a battery!

What this means is that discharged lead-acid batteries are bad news. You need to avoid them like the plague.

So the path was clear: Get a jump start, drive the car for the next hour and half to SFO and hope that the battery gets its life back. Like I said, a professional does not think. He/she reacts.

But a professional also recognizes his/her limitations. In my case, my limitation was that I was really cheap and had not invested in jumper cables or AAA insurance. A professional also typically has no real friends. I knew that none of my "friends" would be willing to stop by to give me a jump at 7 AM.

So I reacted to this problem by taking BART (i.e., public transport) to the airport.

I dont know if you guys encounter this, but sometimes when you have something on your mind it seems like the whole world is starting to think about the same thing. So here I was thinking about sulfation of lead-acid batteries and at this conference on grid storage, there was all this talk about the UltraBattery (this is a trade name) as a means of preventing sulfation. There were actually two talks completely dedicated to it.

I spoke about this advance a little while ago. The concept is to add some carbon into the negative plate when you make the electrodes. Everything else stays exactly the same. But for some magical reason the sulfation decreases significantly.

The talks were showing data where the battery was being cycled a little bit (like a Prius battery does) where the battery without the carbon tanks after a few hundred cycles but the one with the carbon works much better (thousands of cycles). Apparently, the carbon solves the sulfation issue.

There is a variant of this idea which involves connecting the negative plate in parallel to an electrode made of activated carbon. Activated carbon by itself is used to store energy in the double layer (i.e., a double layer capacitor). So essentially you are connecting a battery electrode in parallel to a capacitor electrode in both these configurations.

What was amazing was that they really had no idea why this was happening (although its been a few years since this first came out). DOE is actually funding a project to try to get to the bottom of this advance. Its sad but true- there is a fundamental change in a 150 year old technology but we have no idea why this change occurred.

Some things in life are really hard to reconcile (e.g., is there a God? why does EVERYBODY make more money than Scientists?) but this problem is not in the same class. I believe that this lack of understanding comes down to limited funding for research combined with the "herding" of research topics.

Lead-acid batteries are cheap. The one that I ultimately replaced my car with cost me $165/Kwh. Assuming I got ripped off (is that even an assumption for things car related?) it stresses the point that these batteries are cheap. Adding a few percent of activated carbon to the paste is not going to break the bank. All through the conference I kept wondering why lead-acid's are not being made with a bit of activate carbon to ensure that sulfation is not a problem.

As an aside, the cheapest battery we know of is the lead-acid battery. For grid applications, the thought is that we need batteries that cost less than $100/kWh. Something pretty radical has to happen for us to make these cost numbers. Making batteries the way we have made them in the past will not allow us to get there. But this is for another post.

So would adding a bit of carbon result in the battery lasting the life of the car (say 15 years)? The company that is commercializing this says it could last 7 or maybe 15. Meaning: they have no idea! Problem with not knowing why something works- there is no way to predict how long it will work. Moreover, the data they show is based on Prius-like cycling. My car does not have the same cycling profile. Unless we understand what is going on, we have no way to knowing how changing conditions will change performance.

In time, this data will show up and we will know if we will can make a better lead-acid car battery. But wouldn't it be better if we understood what was going on?

Truth be told, I'm not at all convinced that my battery was sulfated and could have been saved with a timely jump start. It lasted 7 years! That's a long time. Plates corrode and they shed. Maybe I ought not to expect more from my energy storage devices.

But being able control failure modes in batteries is crucial in ensuring that we can move to electric drive. And they will be crucial if we ever want to store the electricity from the sun. Solar panels last 25 years; do you really want to change your batteries every 5 or 7 years?

But to control the failure, you first need to understand them. And in many cases, we don't quite have life of batteries pinned down. They change with chemistry, multiple failure modes occur at the same time, and in some newer chemistries we just haven't had the time to collect the data to see what the failure mode is.

So we have clues and hypothesis for failure, but we can't quite predict failure rates with cycling conditions. There is no cycle/calendar life simulator for batteries.

Actually that is not true. There are many many life simulation tools for batteries. But none of them actually work!

To me this incident highlights the importance of fundamental research to understand real-world problems. There is quite a bit of fundamental research; and there is no dearth of real world-problems. What we don't do enough of is linking the two (The Program at Berkeley is unique in that its the only one that does this in the whole field of batteries).

It also highlights the fact that I really ought to stop being so cheap, spend some money, and get jumper cables.

Venkat

A Brief History of Batteries- Part 2

Last week I posted on the need to understand the history of battery development and how this will influence the future of batteries.  We conclude today with Part 2 of this series. 

Chapter 3:  If it is sparingly soluble, then lets talk. 

The lead acid battery is the first rechargeable battery ever made.  Its endurance over 150 years is a testimony to its robustness (or to the fact that battery researchers can’t seem to find anything better even after 150 years.  It is all a point of view!). 

The lead acid battery undergoes what is called dissolution-precipitation.  This is the mechanism by which charge/discharge occurs in the battery.  Basically, you dissolve the compound in solution and then it precipitates out.

The behavior of the lead-acid battery is remarkably similar to that of the zinc electrode in a Zn-manganese oxide alkaline battery or for that matter to the lithium thionyl chloride battery.

But if the lithium thionyl chloride is not a rechargeable battery and the zinc-manganese oxide is not a rechargeable battery, then why is the lead acid a rechargeable battery? 

This is because the lead sulfate is soluble in sulfuric acid (which is the electrolyte) unlike the lithium chloride.  But it’s not as soluble as the zinc oxide in potassium hydroxide.  

Its solubility is not too much, nor too little.  It’s just right!  It’s referred to as a sparingly soluble salt. 

This feature of having sparing solubility is critical in making a battery that undergoes dissolution-precipitation recharge. 

This occurs because the reactants and the products are right next to each other.  This means that when you go in reverse, there is a high probability that things go back to the same place where they came from.  Not having something move around is a great way to prevent shape change.

Once you understand that solubility is key you begin to understand the decades that were spent on trying to change the solubility of zinc oxide in electrolyte using various techniques.  And you begin to start thinking about ways to encapsulate the zinc.  And you begin to wonder if you should never let the zinc precipitate as zinc oxide and if you should just keep it as zincate by, say, flowing it. 

All these perfectly valid ideas start to make a lot of sense.  What you can’t answer is if these ideas will succeed in solving the fundamental problem with the zinc electrode. 

But we should remember that in general, the lead-acid is not the greatest battery in the world when it comes to recharging.  Think sulfation.   Remember the blog post on battery rules where I Haiku-ed my way to better battery life?  Remember that sulfation occurs in the discharged state. 

The reason for this is also fundamentally connected to this dissolution-precipitation mechanism.  On the one hand, this mechanism allows you to make a good rechargeable battery, on the other hand, it also causes it to die in time. 

Moral of this story:   If you want good rechargebility, dissolution-precipitation is not a good idea, although we may be able to live with it.    

Chapter 4:  And you thought electroplating was easy.

Electroplating has been a gift that has been giving for decades.  Probably the last big development was the via-hole plating of copper for making semiconductor chip interconnects. 

In general, plating something uniformly is not easy, but it’s not an unsolvable problem either.  We do have a lot of smoothly plated stuff all over the place. 

This is until you try plating lithium (and a few other metals, including zinc).   Plating lithium is sort of important because this would be the charging reaction if you want to make your watch battery a rechargeable battery or if you want to make a Li-sulfur or Li-air battery rechargeable. 

People spent much of the 2-3 decades of the last century trying to make a rechargeable lithium (watch) battery.  The last time I check, I was asked to buy a new watch battery and not try to recharge it. 

This is because, in the case of lithium, the plating results in dendrites and lead to shorting of the battery. 

The reason for this starts with surface inhomogeneities that lead to nucleation of the deposition process in one spot, after which ohmic and transport effects lead to further amplification of this inhomogeneity.

That complicated paragraph is tying to tell you that it plates out like a needle sticking out of the electrode.  The needle can puncture through the separator and short to the cathode.  As I keep mentioning in these blog posts, shorting a battery is not a good idea.  Really, it is not.

Same problem happens in the zinc electrode.  Zinc wants to plate out as a dendrite instead of a smooth surface.  Same reasons as above. 

Every electrochemist that learns of this issue immediately thinks of 10 things to try that could solve the problem.   Turns out all 10 ideas probably don’t work.

There have been, literarily, thousands of studies on trying to solve this issue.  The most promising appears to be using a separator that is hard and prevents the dendrite from growing. 

But as of today, we do not have a method to prevent lithium dendrites at room temperature and give us good power capability.  It’s a problem that is still around. 

The moral of this story:  If your battery requires you to plate out a metal, it is probably going to be an issue achieving good rechargebility. 

And if you want to make a rechargeable Li-air or Li-S electrode, getting the lithium to recharge is, I’m pretty confident, a pre-requisite. 

Epilogue:  Rules to live by. 

So how do we make a rechargeable Li-S and Li-air (or zinc-air) battery?

If I knew that I would not be writing blog posts!

But we need to beat three things that history has taught us: 

1.     Avoid electrodes that require a plating reaction. 

2.     If you have a product that is highly soluble, you are in trouble

3.     If you don’t have any solubility, its worse

One can avoid all this by finding systems where no structural changes happen.  Thus were born systems like Ni-MH, Li-ion, and Ni-hydrogen.  These systems have their own problems, but atleast we are starting with something that has certain inherent advantage.   I will elaborate on these problems in the very near future when I delve into the present-day developments in batteries. 

But suffice to say, if you want to make the battery of the future, then you have to beat the three issues listed above. 

Along the way, you may make the batteries of the past also work.  

Venkat