Oh Dear. An Impossible Battery – From An Impeccable Designer

This is one of those “Now wait just one cotton picking minute!” moments.

There’s a battery design being put forward as working better than Lithium Ion batteries. It uses lithium, and that lithium in the redox reaction is turned into… Lithium. What the?…

Of course lots of folks are saying, or, well, really they would LIKE to be saying “No Effing Way!”. Except the designer is the same guy who designed the present Lithium batteries and a great many OTHER batteries in our lives. Something of the God Of Batteries, technically speaking.

So everyone is milling about muttering. Did he finally lose his marbles and it’s time to farm the old coot out, or will this be a Nobel Prize and saviour of humanity? (Or at least any part that benefits from batteries…)

OK, the chain of connection:

I was reading up on the e-cat just to see if it was finally shipping, or finally gone to the pokey as a fraud. (Neither, yet.) They had a story about the battery:

http://www.e-catworld.com/2017/03/20/battery-researchers-mystified-by-new-goodenough-paper-on-solid-state-battery-its-kind-of-like-cold-fusion/

Not to rain on their tag line, but the only way it is “kind of like cold fusion” is that it is hard to understand or believe. Oh, and lithium is involved.

Battery Researchers Mystified by New Goodenough Paper on Solid State Battery (“It’s Kind of Like Cold Fusion”)
Posted on March 20, 2017 by Frank Acland

On February 28th, 2017, the University of Texas at Austin published a press release announcing that a team led by John Goodenough, professor in the Cockrell School of Engineering had made a breakthrough by developing “first all-solid-state battery cells that could lead to safer, faster-charging, longer-lasting rechargeable batteries for handheld mobile devices, electric cars and stationary energy storage.”

John Goodenough is a 94 year-old solid state physicist who is considered to be the one of the key researchers behind the development of the lithium-ion battery.

There has been an interesting response among battery researcher to the published research. An article published on the Quarz website reports how some researchers are somewhat incredulous about what Goodenough’s paper reports. Here are some excerpts and comments:

“It’s what is not stated in the paper that has some of the battery community stumped. How is Goodenough’s new invention storing any energy at all? The known rules of physics state that, to derive energy, differing material must produce differing eletro-chemical reactions in the two opposing electrodes. That difference produces voltage, allowing energy to be stored. But Goodenough’s battery has pure metallic lithium or sodium on both sides. Therefore, the voltage should be zero, with no energy produced, battery researchers told Quartz . . .

“‘If anyone but Goodenough published this, I would be, well, it’s hard to find a polite word,’ Daniel Steingart, a professor at Princeton, told Quartz . . .

“He’s technically made a perpetual motion machine,” said Venkat Viswanathan, a professor at Carnegie Mellon University in Pittsburgh, Pennsylvania . . .

“’It’s kind of like cold fusion. Here is an experiment that is unbelievable,’said Dalhousie University’s Jeff Dahn, a leading researcher whose Canadian laboratory is on a contract with Tesla. ‘There could be a small possibility that it is right.’”

They have links to a couple of references. One where Special People can get the paper, the rest of us just the abstract:

http://pubs.rsc.org/en/Content/ArticleLanding/2017/EE/C6EE02888H#!divAbstract

Alternative strategy for a safe rechargeable battery
M. H. Braga,*ab N. S. Grundish,a A. J. Murchisona and J. B. Goodenough*a

Abstract

The advent of a Li+ or Na+ glass electrolyte with a cation conductivity σi > 10−2 S cm−1 at 25 °C and a motional enthalpy ΔHm = 0.06 eV that is wet by a metallic lithium or sodium anode is used to develop a new strategy for an all-solid-state, rechargeable, metal-plating battery. During discharge, a cell plates the metal of an anode of high-energy Fermi level such as lithium or sodium onto a cathode current collector with a low-energy Fermi level; the voltage of the cell may be determined by a cathode redox center having an energy between the Fermi levels of the anode and that of the cathode current collector. This strategy is demonstrated with a solid electrolyte that not only is wet by the metallic anode, but also has a dielectric constant capable of creating a large electric-double-layer capacitance at the two electrode/electrolyte interfaces. The result is a safe, low-cost, lithium or sodium rechargeable battery of high energy density and long cycle life.

Another to an article explaining why folks are skeptical and cowed and hopeful and baffled, sort of.

https://qz.com/929794/has-lithium-battery-genius-john-goodenough-done-it-again-colleagues-are-skeptical/

Has lithium-battery genius John Goodenough done it again? Colleagues are skeptical

Researchers have struggled for decades to safely use powerful—but flammable—lithium metal in a battery. Now John Goodenough, the 94-year-old father of the lithium-ion battery, is claiming a novel solution as a blockbuster advance.

If it proves out, the invention could allow electric cars to compete with conventional vehicles on sticker price. The improbable solution, described in a new paper from Goodenough and three co-authors, has drawn intense interest from leading science and technology publications. He estimates that the solution could store five to ten times as much energy as current standard lithium-ion batteries. That’s enough to have Google’s Eric Schmidt tweeting about it.

John Goodenough, inventor of the lithium battery, has developed the first all-solid-state battery cells. Promising!

— Eric Schmidt (@ericschmidt) March 14, 2017

However, other leading battery researchers are skeptical, even mystified, by Goodenough’s claim. For his invention to work as described, they say, it would probably have to abandon the laws of thermodynamics, which say perpetual motion is not possible. The law has been a fundamental of batteries for more than a century and a half.

Goodenough’s long career has defined the modern battery industry. Researchers assume that his measurements are exact. But no one outside of Goodenough’s own group appears to understand his new concept. The battery community is loath to openly challenge the paper, but some come close. “If anyone but Goodenough published this, I would be, well, it’s hard to find a polite word,” Daniel Steingart, a professor at Princeton, told Quartz.
[…]
Goodenough towers over the battery world

For almost four decades, Goodenough has dominated the world of advanced batteries. If anyone could finally make the breakthrough that allows for cheap, stored electricity in cars and on the grid, it would figure to be him. Goodenough invented the heart of the battery that is all but certainly powering the device on which you are reading this. It’s the lithium-cobalt-oxide cathode, invented in 1980 and introduced for sale by Sony in 1991. Again and again, Goodenough’s lab has emerged with dramatic discoveries confirming his genius.
[…]
Goodenough reported that his new battery cell had achieved a 10-fold improvement in energy density—the amount of energy stored—in one case, and a three-fold improvement in another. In one experiment, Goodenough estimates a 30-fold improvement on the best density in a lithium-ion battery today—8,500 watt-hours per kilogram. Moreover, this was accomplished not using exotic materials, but cheap sodium and sulfur. That means, unlike many other reported battery breakthroughs, this one could actually be used in mainstream-priced cars.
Still, the paper has baffled battery researchers

It’s what is not stated in the paper that has some of the battery community stumped. How is Goodenough’s new invention storing any energy at all? The known rules of physics state that, to derive energy, differing material must produce differing eletro-chemical reactions in the two opposing electrodes. That difference produces voltage, allowing energy to be stored.

Sidebar headline: “It’s kind of like cold fusion. Here is an experiment that is unbelievable.”

But Goodenough’s battery has pure metallic lithium or sodium on both sides. Therefore, the voltage should be zero, with no energy produced, battery researchers told Quartz.

Goodenough reports energy densities multiple times that of current lithium-ion batteries. Where does the energy come from, if not the electrode reactions? That goes unexplained in the paper.

Now somewhere in all the links I went past in the originals, I ran into this link:

https://medium.com/the-unfortunate-tetrahedron/a-potential-big-deal-in-batteries-298c7ad9543a

Now every so often you run into someone with clarity of thought, who keeps a tidy mind, clearly understands their subject, and writes well. This is one of those people. Read the article. I can’t improve a bit of it. ( I do love tidy minds… and this one is well trained too ;-)

Unfortunately, he too arrives at the point of saying it just can’t be, but seems it ought to be. Sort of.

Dan Steingart
Assistant Professional Do Nothing Ne’er Do Well
Mar 3

Redox without Redox

Recently Braga et. al. published Alternative Strategy for a Safe Rechargeable Battery in Energy and Environmental Science. This is a subtle title for a work, if reproducible and truly invoking the mechanism described in the article, will have a lasting impact on the battery community. As described, however, it seems to violate key concepts in thermodynamics, namely the conservation of energy.

The big idea is motivated halfway through the paper. The claim is that of anomalous capacity at the cathode:

The measured capacity was much greater than the capacity of the sulfur in the cathode, but it corresponds to 90.1% of the capacity of the lithium anode, which is much greater than the capacity of the sulfur. We therefore conclude that the sulfur acts as a redox center determining the voltage of the cell at which electrons from the anode reduce the Li+ at the electrolyte/cathode interface to plate lithium rather than reducing the sulfur, so long as the voltage remains above 2.34 V; below 2.34 V, the S8 molecules are reduced to Li2Sx (1 < x 2.34 V, the cell is rechargeable and the sulfur is not reduced. The Fermi level of the lithium plated on the carbon–copper composite cathode current collector is determined by the Fermi level of the cathode current collector, whereas the Fermi level of the lithium anode remains that of metallic lithium, but the cell voltage is determined by the energy of the redox couple of the unreduced redox center.

In short: the potential of the cathode is set by the chemical species of the cathode interface, but the capacity of the cathode is set by the lithium anode. If this is correct this is a big deal, as described further along:

These illustrations demonstrate that the ability to plate/strip an alkali-metal anode in contact with a Li-glass or Na-glass electrolyte allows a totally unconventional strategy for the design of a rechargeable battery in which reversible plating of an alkali metal from the anode onto the cathode current collector gives a battery cell having a capacity determined by the amount of alkali metal used as the anode rather than the solid-solution range of the working ion in a host cathode lattice. The voltage is limited by the difference in the chemical potential of the alkali-metal anode and that of the cathode current collector, but it is determined by a cathode redox energy (if one is needed) that is above the Fermi level of the metallic cathode current collector. Without a redox center, the voltage is V = 3.5 V.

Long story short the effective energy density of a battery, if this can be utilized to its full extent, approaches 8x the current energy density of lithium ion cells (based on our current understanding of electrodes the projected ranges is somewhere between 2 and 5 times modern lithium ion capacity).
[…]
Everything I understand about chemistry and thermodynamics says this is impossible. Can the limit really be the total capacity of the anode without any thought to the configuration of the cathode? Figure 4 in the paper suggests a mechanism and opens a bunch of questions. Below are my notes for working through this:

I’ll leave you to hit the link and read the rest, along with a nice pretty picture.

So all in all I’m left where I started. Holy Cow! mixed with “So where did they screw up?”.

FWIW, that last site also has a great writeup of design tradeoffs in batteries (that seems to be their major focus in that “unfortunate tetrahedron” that makes their site name…) If you have any interest in battery design or even extensive use, this is a very readable and very correct description of what all you need to think about, in very approachable language, in the design of batteries. (Along the way it manages to illustrate the problem facing vehicles in trying to replace gasoline as an energy storage system…)

https://medium.com/the-unfortunate-tetrahedron/the-unfortunate-tetrahedron-ce1e44d0b961

I found this image especially illustrative, though it only makes up one edge of the tetrahedron.

The Ragone Plot

The Ragone Plot

But there are at least two major factors in batteries not addressed by this plot, and one is hidden in plain sight. We’ll start with that.

The Ragone plot shows energy vs. power; dimensional analysis shows that the diagonal lines must in the units of time, specifically charge or discharge duration. Point 3 tells us that for a given application duration at a given power drain we need a certain size of battery. In a perfect world we multiply power by time to figure out what the battery size should be, in an imperfect world Ragone corrects for this.

Hidden deeper is an existential concern. Upon first glance, all things being equal there is no reason not to want to hang out on the upper right. However, consider a device that can provide upwards of 400 WHr/kg in under 36 seconds. This could either be

1. a great battery or
2. a mediocre bomb

Gotta love that writing style and clarity.

This is but a small excerpt of an excellent article on the battery design space.

So there you have it. A battery that moves lithium (or sodium) through a glass electrode and makes it into… lithium, but because it is NEAR something else, it (wave wands and hands) makes electricity. But nobody really can say for sure why it works… except maybe one guy, who isn’t quite illustrating all the magic enough for the mere mortals to get it just yet.

Secondly, a very skilled mere mortal who also isn’t getting it; but is clearly also a tidy mind keeper and highly skilled in batteries.

All in all an interesting little “cannot be but seems to be” conundrum.

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About E.M.Smith

A technical managerial sort interested in things from Stonehenge to computer science. My present "hot buttons' are the mythology of Climate Change and ancient metrology; but things change...
This entry was posted in Tech Bits and tagged , , , , , . Bookmark the permalink.

26 Responses to Oh Dear. An Impossible Battery – From An Impeccable Designer

  1. A C Osborn says:

    Is this in actual fact acting as a slow release Capacitor rather than a battery?

  2. pearce m. schaudies says:

    Hi Chief. It has been 50 years Since I studied statistical thermodynamics. Him talking about Fermi level makes me think it’s a quantum mechanic Trick. First let’s assume he’s not breaking any laws of anything. Second how would you go about making a quantum mechanical battery. Or capacitor.

    First …

    but also has a dielectric constant capable of creating a large electric-double-layer capacitance at the two electrode/electrolyte interfaces. 

    … and …

    The Fermi level of the lithium plated on the carbon–copper composite cathode current collector is determined by the Fermi level of the cathode current collector, whereas the Fermi level of the lithium anode remains that of metallic lithium, but the cell voltage is determined by the energy of the redox couple of the unreduced redox center.

    The rest of the solution is left as homework for the student. Show your work. I suggest getting serveral smart people in a room and asking them how many different ways can you think of for this to happen.

    Regards,
    Pearce M. Schaudies.
    Minister of Future

  3. Pretty important here is the mention of workfunctions, which are effectively the “sucking power” of a material for electrons. The workfunction of a material is affected by the local environment – what else is there at the same time. Though I still can’t see precisely how this battery works (not enough solid information, unsurprisingly) there’s at least a clue that it can work and that there is an energy-change, and thus it can store and release energy by changing the local environment of the Lithium atoms. Goodenough has a great track-record of getting things right, too, and is a very bright person.

    Instead of storing energy as chemical bonds, he’s storing it as a difference in electron-affinity. A bit of lateral thinking as regards how energy is actually stored.

  4. p.g.sharrow says:

    In the comments at the first link:
    ” jimbo92107 • 2 months ago

    “Wow, I just read the paper on this new battery technology. Notwithstanding my abysmal ignorance of the math, the approach makes sense. He has eliminated the dendrite problem by creating a glass “electrolyte” doped with atoms of the chosen anode. This means that he can achieve ion migration THROUGH THE GLASS without a wet electrolyte! The lithium or sodium atoms push their brothers through the glass in the either the charge or discharge direction, all in a solid state. Dendrites are prevented because they have nowhere to grow, as the anode/electrolyte/cathode layers are all solids, pressed together in an air-tight package.”

    Jimbo generally pays attention.
    This sounds to me to actually be a super capacitor. The energy is actually dielectric warpage in the sintered glass separators. Doped glass is likely the key between the pure metal plates…pg

  5. andysaurus says:

    ( I do love tidy minds… and this one is well trained too ;-)

    I just had a look on Linked in, and the guy you reckon has a tidy, well trained mind appears to be Assistant Professor at Princeton University, so one would hope so. His short comments indicate his interest in batteries so he is probably the right guy.

  6. wizz33 says:

    if you want a sci paper use the chrome plugin from http://sci-hub.cc/

  7. gallopingcamel says:

    I don’t see why the pundits have their knickers in a twist.

    What jumped out at me was the idea of using a solid electrolyte instead of a liquid one. You still need an anode and a cathode made out of materials with different Fermi levels just as I learned in high school 70 years ago.

    The fraudsters at E-cat world try to muddy the waters by suggesting that fusion reactions are taking place. Nobody should take that seriously.

  8. tom0mason says:

    My first thought are that when charged the lithium has one type of crystal orientation and as it discharges the lithium moves to different crystal orientation. However I am very limited in my knowledge on this subject and certainly of lithium’s crystallography but could this be the ‘trick?

    So far the only papers I can find on Lithium having different crystal structures all are at very, very high pressures. e.g https://www.researchgate.net/publication/7671313_Phase_Stability_and_Broken-Symmetry_Transition_of_Elemental_Lithium_up_to_140_GPa

    and https://www.researchgate.net/publication/44050925_Dynamics_of_elemental_lithium_at_megabar_pressures

    Ho-humm probably another logical misdirection…

  9. R. Shearer says:

    The lawsuits between Rossi and Industrial Heat are still in a pretrial stage, but it appears that fraud committed by Rossi is being revealed. http://ecat.org/2017/ih-expert-witness-publishes-scathing-e-cat-report/

  10. philjourdan says:

    From the sound of it, the development will not cost a fortune. So it will either work or not. If it works, then the world of Physics has a lot of “splaining” to do, and it could be a major breakthrough in that field as well.

  11. pouncer says:

    tomo says: “My first thought are that when charged the lithium has one type of crystal orientation and as it discharges the lithium moves to different crystal orientation. ”

    Yeah. Without any math at all I’m analogizing the situation to phase changes in water / ice or liquid ammonia / gas. It’s “lithium” on both sides of the reaction but energy is being pumped from one side to the other, charged by outside forces, and that energy can be released from the high side, to affect the OUTside, and come to rest on the original “low side” without ever reacting with another chemical.

    By definition, a catalyst allows or affects the rate of chemical processes without actually being contributing bits to the product. That sort of thing is not considered miraculous or a violation of fundamental physics. Here it appears to be claimed that different catalytic environments around the cathode versus the anode allow different energy states to develop in identical substances at the two non-identical locations. If the switch is thrown to reverse charge, reversing cathode and anode, then energy states will attempt to relax or revert and current will flow.

    Analogies aren’t science. I am no doubt completely up the wrong tree, here. But I’m not seeing anything in the write up that suggests perpetual motion, either.

  12. E.M.Smith says:

    I doubt it is a capacitor. Spacing between layers too large, and we already make physically better supercapacitors that don’t come close to the rating they claim.

    I think the clue is in the V vs Sulpher behaviour, but don’t know what it means. Perhaps pushing electrons into unusual orbitals? Who knows.

    I think we will know in time, but hope it isn’t too long…

    Also, there doesn’t seem to be a lot of secret sauce, so replication ought to be quick.

  13. Terry says:

    “lithium in the redox reaction is turned into… Lithium”

    Simple….DI-LITHIUM crystals

  14. Wayne Job says:

    “There are more things in heaven and earth Horatio” We have yet to scratch the surface of what is possible. Good on this old geezer Goodenough, if it works it is the beginning of some new science, much like what follows. https://vimeo.com/214639880 if a password is needed it is force5 this also is new science that does not fit.

  15. jim2 says:

    Some battery ingredient has to change oxidation state to work. I tried signing up for the free logon at RS, but the logon doesn’t work. I’m with CIO on this one, it must be the sulfur if lithium doesn’t change state, net-net.

    The weird part of the claim appears to be that Li+ reacts with sulfur in a novel manner, not forming the ionic compound, Li2S. There are odd bonds such as the coordination bond, but lithium has no higher level electron levels that are both shielded by other electrons and empty. Could sulfur be sharing an electron with lithium without moving all the way to the lithium ion? And why would it NOT form the ionic compound? What would stop it?

    Here is a more conventional Li-S battery:

    http://www.sionpower.com/pdf/articles/SionPowerECS.pdf

  16. tom0mason says:

    Back in 1978 we dreamed of many impossibilities and they have come to pass…
    http://unesdoc.unesco.org/images/0007/000748/074804eo.pdf

  17. Power Grab says:

    I have the full article.

  18. cdquarles says:

    EM, I think that I’ve said this before. With a battery, never forget the electrolyte. The standard half reactions we know of may not be where the action is really happening.

  19. Graeme No.3 says:

    IF the lithium isn’t changing and the normal rules of chemistry and physics apply then we might look at the other materials in the battery, sulfur and copper – can they be reacting? Lithium acting as a charge transfer agent.
    I notice the big variation in the mesurement of properties. 3 times the power density of a ‘standard’ Lithium cell is vey useful but not revolutionary. 10 times would be astonishing and wonderful, but I think the final advance would be closer to the first figure.

  20. Jon K says:

    I have the .pdf of the original paper if you would like me to email it to anyone, just provide email. This was also cited in 3 other papers. I can get those too if anyone is interested.

  21. E.M.Smith says:

    @Jon K:

    Perhaps you could just let us know if the paper has something to better explain the Li vs Li or if it just uses the same Fermi Level statement?

  22. Jon K says:

    @ EM
    I can’t add anything to Dan Steingart’s analysis with my level of knowledge and I didn’t see anything that better explained the reaction.

  23. tom0mason says:

    A skeptical review of what has reported about the battery is here —
    http://lacey.se/2017/03/29/on-the-skepticism-surrounding-the-goodenough-battery/

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