Showing posts with label Batteries. Show all posts
Showing posts with label Batteries. Show all posts

Friday, June 13, 2014

"Where's my F*cking Electric Car?!"

I've been maintaining a pretty good clip on this blog of about new 3 posts a week ("not bad," thought the novice blogger to himself)...until two weeks ago. Since then I've been very wrapped up with work and had to focus on that whole science thing. The problems we're working on are very nuanced, but not unknown in the field of electrochemistry, which itself is a relatively new field. Basically, electrochemistry is hard, and few people outside of the science understand just how hard it is (hence the title).

Electrochemistry emerged as a separate field of chemistry after early scientists first started laying the groundwork for general electromagnetic theory and chemistry. Elements were discovered, conservation of mass and matter were accepted, electrostatic generators were built, and electrical detectors were invented all before scientists even started tinkering with electrochemistry. And the first steps were pretty gruesome. In 1800, an Italian doctor (Galvani) dissecting frogs was able to make dead muscles twitch by touching them with different metals connected to each other in series. A physics professor (Volta) disagreed on the mechanism and arranged stacks of different metals and brine-soaked paper to achieve similar results. This was the invention of the battery: the first device that turned chemical energy into electricity, but no one at the time knew how it worked. That didn't stop anyone from using it though; application outpacing understanding in the energy field has been the MO since the battery was first invented.

Electrochemistry got its first big scientific break from Michael Faraday in 1830s linking current (amount of electricity) and the amount of matter deposited during electroplating experiments. It took another 90 years and the framing of modern thermodynamics by Willard Gibbs before the groundwork of analytical electrochemistry was laid by Hermann Nernst relating voltage to chemical equilibrium. So only in the last decade of 1800 are we even able to discuss the describe the designed properties of a battery in simple terms of voltage and current.

So...electrochemistry took a while to get to a point where we can actually analyze it. So what? Shouldn't it have erupted in discovery after discovery since then? Not really. Most of the batteries we use today were invented long before anyone really understood what was going on. Even the modern lithium ion battery, invented in the 1980's, features a component called the "solid-electrolyte interface" (SEI) that sets the longevity and safety of lithium ion batteries, however scientists have only recently began to understand the structure and composition of it. In other words, the microns-thin layer that determines how long you can use a battery and whether or not it will burst into flames is the least understood part. There's almost too much that goes into the design of a practical battery not to take a trial-and-error approach. There's:

  • The electrical potential of the positive and negative electrodes (sets the cell voltage)
  • The chemical kinetics of the reactions at the positive and negative electrodes (helps determine maximum current)
  • The structure of the electrodes (determined by the conductivity of the reactant species and the speed of the kinetics)
  • The electrolyte composition and properties. This can be further broken down into:
    • Operating pH (determines chemical compatibility with battery housing, electrodes; also determines prevalence of undesired side reactions)
    • Conductivity (helps determine maximum current)
    • Organic vs. Aqueous (determined by cell voltage, cost considerations, and storage reactions)
  • The membrane separating the positive and negative sides of the battery (critical component, helps determine a lot of things)
    • Cell durability
    • Cell efficiency
    • Maximum current draw
    • Cost and manufacturability
    • Operating temperature regimes
  • Cell housing and architecture
    • Sealed vs. Flow (flow batteries limited to liquid energy storage reactions)
    • Bipolar vs. Monopolar (tradeoffs on manufacturability)
This is by no means an exhaustive list. To give an idea of how all these parameters fit together, I'll walk through an example in another post where we'll go from chemical fundamentals to full cell operation. During that exercise, it'll become pretty clear that we're lucky to have even what we have now given how easily things can go wrong.  

Wednesday, May 21, 2014

If It Sounds Too Good To Be True...

My job is working for a battery startup as an electrochemical engineer. My day-to-day is spent being elbow-deep in the science of batteries. It's difficult work (really difficult; I'll write about it one day), and I'm always learning something new. From time-to-time, a friend or I will come across an article about a new battery chemistry. I've come to learn through many examples that if it sounds boring (silicon anodes, or quinone electrolytes), it's usually big news, but if it sounds exciting (a battery that runs on air! an edible battery!), it's usually not great.

The Power Japan Plus battery is one of those not-so-great batteries, and here's why:

Lithium ion batteries work by shuttling ions between two "intercalation materials." The lithium rests in the crystal structure of a lithium oxide at discharge, then upon charging, shuttles that lithium from the lithium oxide, through the lithium salt electrolyte, and inserts it into the open spaces of a graphite anode, thereby storing energy. The "Ryden battery" is a similar lithium intercalation battery, except that the source of the lithium isn't a lithium oxide, it's the lithium salt electrolyte; there is no solid state source for lithium ions [1]. As such, the capacity of the battery is limited by how much lithium you have in the electrolyte, which is a function of volume and concentration. You don't want to have a large volume of electrolyte because that means it's a greater distance the lithium ion has to travel, increasing ionic resistance, and driving down cell efficiency. Therefore we have identified one limit to cell capacity.

Even if you manage to have an exceptionally high concentration of lithium (you can't, btw; it's stuck around 1M for safety considerations [2]), you're still limited by the specific capacity of graphite, which is the bottleneck in current lithium ion chemistries at around 100-150mAhr/g. Power Japan Plus gives us a diagram showing cell voltage as a function of capacity and the battery stops charging at 140mAhr/g; just what we'd expect. Here is another limit to cell capacity (granted a limit we come across all the time in lithium ion batteries).

Finally, all this talk about lithium intercalation into graphite wouldn't be possible unless we had a counter-reaction to balance the charges. The "Ryden battery" claims to use a negative ion intercalating into graphite as the cathode. There are a couple of ions that could do this but ones that comes to mind are halides like fluorine or bromine (I actually couldn't find much literature on the electrochemistry of negative ion intercalation compounds: a bit of a red flag actually). We have other evidence to think this might be the case: Power Japan Plus has a cell voltage of around 4.5V. Solid state electrochemistry is very different than aqueous chemistry, but it still follows similar trends; in order to get a cell voltage that large with lithium on one side, you need a very electronegative electrochemical couple. Fluorine or bromine will do it. In an aqueous system (which is impossible for materials compatibility reasons, but for this exercise let's go ahead and consider it), a LiF battery would have 5.8V, which is close to what the "Ryden battery" is. And fluorine is often featured in lithium ion battery electrolytes, adding support to our guess that the other couple is a halide. This goes against their idea that their all-cotton battery is earth friendly if it contains one of the most poisonous elements on the periodic table. I'm not faulting Power Japan Plus for their chemistry; I'm faulting them for their messaging. If they think cotton in a 3000C furnace (which is just carbon at that point) and fluorine are "earth friendly" then who am I to argue. 

The long and short of this analysis is we have a battery that has the same fundamental limitations as lithium ion batteries (the graphite anode), with a cell architecture that has serious capacity limits, and questionable negative electrode chemistry. 

I don't mean to be a killjoy, but energy storage is a serious problem that demands serious answers. This is not one of those serious answers; let's stop treating it that way.

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[1]: http://powerjapanplus.com/battery/equation.html
[2]: http://www.electrochem.org/dl/interface/sum/sum12/sum12_p045_049.pdf