
Has Li-battery genius John Goodenough done it again? Colleagues are skeptical - M_Grey
https://qz.com/929794/has-lithium-battery-genius-john-goodenough-done-it-again-colleagues-are-skeptical/
======
logfromblammo
From what I understand of this, the battery works like this:

You have a sodium or lithium metal anode, and a sulfur-carbon "ink" cathode on
a copper charge collector. The battery is encased in steel, so a cross section
would be steel-Na|Li-glass-S (aq)-copper-S (aq)-glass-Na|Li-steel. The anode
has to be sealed away from oxidizers and water, or it will react violently
with a direct chemical reaction rather than through the desired
electrochemistry.

During discharge, at the anode, the reactive metal violently throws its extra
electron away as hard as it can, because it _hates_ having that extra one. It
_really, really_ wants to have +1 charge. The steel casing doesn't help, but
that glass electrolyte is apparently porous enough that +1 ions can pass into
it. So the lithium/sodium throws an electron down the wire and jumps into the
electrolyte, because positively charged ions repel each other. That works fine
until the electrolyte fills up all those empty spaces with positive ions. The
anode can't throw any more electrons down the wire, because positive ions have
nowhere to go, and attract the electrons right back out of the wire just as
strongly as the atoms could throw them.

On the cathode side, electrons are coming in from the wire, spreading out
across a copper plate, and jumping onto sulfur atoms, which devour extra
electrons with a passion. Sulfurs _love_ to have 2 more electrons than they
usually own. Sulfurs near the copper plate devour two free electrons and
become [S]--. It just so happens they live in a thin "ink" cathode, and are
therefore very close to the positive ions that have been filling up the
electrolyte when they become charged. They get yanked across to the glass.
Ordinarily, if all this happened in an aqueous electrode, each negative sulfur
ion would coordinate with the two positive ions in solution so that the sulfur
can keep its extra two electrons, and the lithium or sodium wouldn't have to
take back their hated extra. The glass-aqueous interface probably prevents
this?

I would guess that the glass electrolyte allows so much positive charge to be
present in it, without allowing the sulfur inside, that as soon as the sulfur
hits the glass, it fumbles its extra electrons that fly out of its grasp and
home in on one of the positive ions, converting it back to neutral metal.
Sulfur grumbles and goes back to the copper to pick up another pair. Repeat
until the positively charged layer in the electrolyte is not strong enough to
yank the electrons off of sulfur, and it hangs on to its electrons at the ink-
glass interface. The battery is now fully discharged. Physically, you have
layers Li, [Li]+ (glass), Li (glass), [S]-- (aq), Cu. I'm guessing here, as I
haven't read the paper.

During recharge, you are pushing electrons into the anode and pulling them
from the cathode. That reactive metal wants nothing to do with extra
electrons, so it starts attracting positive ions back through the electrolyte
toward the metal anode. Meanwhile, that copper plate is having electrons
sucked out, getting positively charged, and yanking the sulfurs across to take
their borrowed electrons back. The neutral sulfurs can then wander back to the
glass and grab electrons from the reactive metal in it. They shuttle the
electrons back and forth, turning the metal on the cathode side of the glass
back into ions that transport back toward the anode. Eventually, the
electrolyte is once again saturated with only positive ions, and the battery
is fully charged. As soon as the charge is removed, the atoms in the anode
will once again try to throw away their extra electrons and escape into the
electrolyte.

It seems important that the glass electrolyte be constructed such that the
cathodic atoms and ions cannot enter it. While the battery is charging or
discharging, those will be bouncing back and forth like ping pong balls in a
Chinese recreation center, shuttling electrons between the glass-ink interface
and the ink-copper interface. The action of the battery is allowing the
reactive species to ionize, and get their charges closer together, but not so
close that they can coexist in the same ionic crystal or aqueous solution.
That would make it too difficult to separate the charges again, to recharge.

Of course, as I am not a chemist, I might be completely wrong about this.

~~~
dotancohen
This is going to be my children's bedtime story tonight. Thanks!

~~~
oliv__
Fun times

------
dmoy
Previous discussion:
[https://news.ycombinator.com/item?id=13778543](https://news.ycombinator.com/item?id=13778543)
Maybe some additional added detail in this qz.com article, idk.

~~~
Recurecur
There are some odd disparities between the UT article and this new article.
The UT article claimed:

"The use of an alkali-metal anode (lithium, sodium or potassium) — which isn’t
possible with conventional batteries — increases the energy density of a
cathode and delivers a long cycle life. In experiments, the researchers’ cells
have demonstrated more than 1,200 cycles with low cell resistance."

That would seem to completely rule out the lithium-air explanation.

Regarding the mechanism for energy storage, the UT article said:

"The engineers’ glass electrolytes allow them to plate and strip alkali metals
on both the cathode and the anode side without dendrites, which simplifies
battery cell fabrication. "

Does the "plating and stripping" language imply energy storage/discharge?

The abstract from the paper itself reads:

"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."

It is also referred to as a "metal-plating battery" in the abstract. I find it
mystifying that neither of the terms "plate" or "plating" appears in the
Quartz article.

------
cr0sh
I hope they're doing more than just arguing over whether it works or not.

Assuming there is enough information in the paper to replicate the experiment,
then the proper course of action would be re-run the experiment and see
whether the counter-hypothesis that this won't or can't work is true or not.

Of course, other groups should also do the same. I just hope this isn't
another case of "we can't afford to do a replication of the experiment because
that doesn't get us grant money" \- which I have read about elsewhere is a big
deal right now in scientific research (that is, new research is not being
replicated - thus science isn't really being done properly).

This research, if it does turn out to be valid, could or would be world
changing.

~~~
omginternets
Not that you're completely wrong, but it's worth recognizing that experiments
aren't exactly trivial to replicate. There's a (sometimes _massive_ ) cost in
time and money, and expertise can get unbelievably niche.

It's really not as simple as "just replicate it".

~~~
Mithaldu
I've seen discussions about replication a lot. Isn't it more often than not
the case that replication is made expensive because the paper describing it
simply leaves out too many details, making replication more of a guessing
exercise than actual, well, replication?

~~~
semi-extrinsic
Well, yes and no. Yes, to a certain extent papers don't have enough details
for replication, but this is mainly because you just can't fit enough details
into the scope of a journal paper. In a PhD thesis, you should be able to.

And no, it's not that replication becomes a guessing exercise, but it's the
fact that the time spent setting up, debugging and then running a replication
of even a perfectly described benchtop-style experiment costs much much more
than the actual equipment involved. And the ROI is poor, since replication
studies are hard to publish.

~~~
btilly
_Should_ , sure.

But there can be critical details needed to replicate which the experimenter
didn't realize were important and didn't think to record. And possibly didn't
notice.

One of the reasons why replication matters is that it is a way of discovering
these factors which matter but weren't obvious.

------
roywiggins
> 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.

"A fundamental of batteries", yes, but also just, well, fundamental of
everything.

~~~
tonmoy
Well, perpetual motion is not impossible, obtaining energy from it impossible

~~~
fmihaila
> Well, perpetual motion is not impossible, obtaining energy from it
> impossible

This is incorrect.

From Wikipedia [0]: _" A perpetual motion machine of the third kind is usually
(but not always)[10] defined as one that completely eliminates friction and
other dissipative forces, to maintain motion forever (due to its mass
inertia). [...] It is impossible to make such a machine,[11][12] as
dissipation can never be completely eliminated in a mechanical system, no
matter how close a system gets to this ideal (see examples in the Low Friction
section). "_

[0]
[https://en.wikipedia.org/wiki/Perpetual_motion](https://en.wikipedia.org/wiki/Perpetual_motion)

~~~
Jach
Parent is probably referencing
[https://en.wikipedia.org/wiki/Time_crystal](https://en.wikipedia.org/wiki/Time_crystal)
_Because a time crystal is a driven (i.e. open) quantum system that is in
perpetual motion, it does not violate the laws of thermodynamics... does not
produce work...does not spontaneously convert thermal energy into mechanical
work...cannot serve as a perpetual store of work... A time crystal has been
said to be a perpetuum mobile of the fourth kind: it does not produce work and
it cannot serve as a perpetual energy storage. But it rotates perpetually._

~~~
roywiggins
In theory I think a closed system undergoing completely reversible processes
could be considered perpetual motion (being reversible, entropy never
increases). The second law states that those are the only sorts of isolated
systems that don't gain entropy over time.

[https://en.wikipedia.org/wiki/Second_law_of_thermodynamics](https://en.wikipedia.org/wiki/Second_law_of_thermodynamics)

But time crystals aren't perpetual motion just by dint of not being closed
systems at all, so they're kind of neither here nor there.

~~~
greghatch
> But time crystals aren't perpetual motion just by dint of not being closed
> systems at all, so they're kind of neither here nor there.

Literally!

------
gene-h
My money is on it being an air battery, in the paper they commented: "The
charge and discharge voltages show a good coulombic efficiency over 1000 h;
the cycling was continued beyond 46 cycles despite an imperfect seal of the
cell. "

A rather simple test to determine if it is in fact behaving as an air battery
would be to weigh the battery before and after discharge. Air batteries get
heavier as they discharge.

~~~
dnautics
you could also try running it in various vacuums.

~~~
sand500
Or in a noble gas environment.

------
hwillis
I had a highly upvoted comment on the original submission- the thing I missed
was that in the original paper they claim they went from metal lithium on the
cathode to metal lithium on the anode after discharge. You can't do that. In
order to have a battery the lithium has to move from a high energy state to a
low energy state- not from one state to the same state. There is something
fundamentally fishy about the experiment, but I'm not sure what. The way it is
portrayed in the paper, you could basically just switch the cathode and and
suddenly have a fully charged battery.

~~~
logfromblammo
If you had a normal electrochemical cell, with a sodium anode and sulfur
cathode, and liquid electrolyte, the sodium would release an electron into the
circuit and hop off the solid anode into the liquid electrolyte. On the other
side, sulfur would grab electrons from the circuit and hop off the solid
cathode into the liquid electrolyte.

In the middle, the ions would keep their charges and physically arrange
themselves such that the charges are balanced in every direction. This would
be an energy minimum, and it would be hard to reverse. Trying would probably
cause the electrolyte to decompose instead of redepositing the original
reactants onto their electrodes. It would not be rechargeable.

As a physical metaphor, you have two mutually-attracted boulders rolling down
from opposite ridges into the same bowl-shaped energy valley. When they
collide, they strike with such force they turn to sand.

In the rechargeable battery, you prevent that last step by putting a giant
springy foam block in the center of the valley, so that the boulders can't
touch. You prevent the sodium and sulfur from coordinating physically to
cancel out the physical force from separated charges. Then to recharge, you
tow or push the boulders back up the hill.

I think the "same metal at the cathode" might be an artifact of putting the
springy foam block in to keep the boulders intact. You couldn't switch the
anode and the cathode any more easily than you could swap the elevations of
the ridges and the valley. That is, it takes as much energy to do the physical
rearrangement as it would to charge the system electrically.

~~~
hwillis
To follow your boulder/hill metaphor, the lithium boulder rolls down the hill
(crosses the electrolyte), settles at the bottom of the valley (bonds
sulfur)... And then somehow as more lithium rolls down the hill, it continues
to pile up at the bottom until it forms another hill, the same size as the
first (lithium plates onto the anode). That's what they claim happens- that
the sulfur acts as a redox center and sets the voltage for an unlimited amount
of lithium. But a redox center cannot just lower the voltage of an arbitrary
amount of metal. The metal is an entirely normal bond and can be cut with an
energy proportional to mass^(2/3), while the energy stored increases linearly.

------
mratzloff
If you're even the slightest bit interested in this topic, I highly recommend
the Nova special "Search for the Super Battery" that aired in February, hosted
by David Pogue.

[https://www.youtube.com/watch?v=pCDuM_apIg8](https://www.youtube.com/watch?v=pCDuM_apIg8)

~~~
nvk
Wonder why they didn't mention LiFePo4. Amazing, non explosive production
cells. A bit pricier, but not that much.

~~~
jpm_sd
The energy density (Watt*hours per kg) is about half compared to the
"explosive" cells on the market.

------
jpm_sd
Honestly, it doesn't matter to most of us right now. Goodenough's original
breakthrough didn't hit the mass market for 20 years. Turning breakthroughs
into /products/ is still really, really hard.

~~~
mrob
Better battery technology increases demand for batteries. Lithium ion
technology made batteries good enough to be common but not good enough for
everything we want to do with them. There's so much battery dependent
technology now that another breakthrough could be even more profitable.
There's strong incentive to get it to market quicker than 20 years.

------
scythe
All-solid-state Li-S batteries have been previously reported by ORNL.
Manufacturing is the giant hurdle here.

------
6stringmerc
Very interesting. I remember how many entries to the LITECAR challenge
essentially said "Use graphene!" as the innovation, which, frankly speaking,
is fundamentally useless. As in, it doesn't really exist as a viable notion
right now, or for the foreseeable future in consumer application.

I like how the article notes one of the primary benefits is related to cost,
which always is a concern of mine when reading about innovations and
developments and discoveries like this.

All that said, I'd really like to see what a catastrophic failure looks like,
because if they're going to be on the road eventually, let's see what we're in
for in some worst-case-scenario testing.

------
nmc
I have the same intuition about this that I had when the OPERA team thought
they had exceeded the speed of light [0] -> this violates a fundamental law of
physics so this must be wrong.

My money is on experimental error.

[0]: (most upvoted HN post if you search for "speed"+"light")
[http://www.bbc.co.uk/news/science-
environment-15017484](http://www.bbc.co.uk/news/science-environment-15017484)

------
Mizza
If there is a theory that the battery is in fact a Lithium-air battery,
couldn't this be easily disproved by running the experiment in a vacuum?

~~~
zkms
Or just under an atmosphere of inert gas.

------
amai
The use of glass in this invention sounds similar to this one:
[https://phys.org/news/2015-03-glass-coating-
battery.html](https://phys.org/news/2015-03-glass-coating-battery.html)

------
neutronicus
"Goodenough" is a very apt name for a leader in battery technology.

~~~
thanatropism
Life lesson: John Goodenough is certainly happier than Pete Best.

~~~
noiv
Isn't it strange good enough sells better than the best?

~~~
syncsynchalt
As any HN reader should know, Worse Is Better
([https://en.wikipedia.org/wiki/Worse_is_better](https://en.wikipedia.org/wiki/Worse_is_better))

------
wfbarks
Seems like a pretty good battery, but is it goodenough?

------
callesgg
I am hopping for some experimental verifications :)

------
csours
TLDR; Batteries store electrical energies by using materials with different
potentials. The paper in question does not indicate materials with different
potentials, at least as far as others in the battery field can see.

1\. _unlikely_ \- the paper is a complete fraud

2\. Some sort of measurement error has occurred (possible)

3\. The method of action is different from what is described in the paper

4\. The method of action is novel

~~~
canada_dry
Good synopsis.

Given the pedigree of scientists involved my money is on #4.

~~~
hwillis
I'm skeptical. The conclusions drawn in the first paper were... egregious. I
think its more likely that there was insufficient oversight. I'm reminded of
the FTL neutrino experiment.

~~~
greglindahl
It's definitely an extraordinary claim. Even people excited about the
possibilities should be tempering their expectations.

~~~
logicallee
do researchers not have professional courtesy to do something like replicate
an experiment without publishing the experiment it was based on (without
letting the cat out of the bag)? (I mean if they were approached to do so by a
researcher with an extraordinary result.)

What I mean is if someone across the world sent you a detailed methodology to
test, without mentioning the result you're expected to get, would you do it
for them without wanting coauthor credit, and without talking to anyone else
about it?

~~~
hwillis
No. A project lead doesn't (usually) do all of something personally, so
outside of large personal favors you'd be asking someone to have people under
them do a ton of work to replicate something for no tangible benefit. At most
you get a special mention, or very rarely are added to the author list.

Replicating experiments requires extremely expensive equipment, materials,
expertise and time. You can't bang out most experiments in a few afternoons.
If you want to have your results replicated you do them again, because you're
gonna be fastest and you're the only person you know 100% will follow the same
steps.

~~~
logicallee
Thanks. This makes sense.

Now that it had been published, are teams going to try to replicate and
understand it? Or are some seeming breakthrough papers ignored because they
"must" be wrong?

~~~
hwillis
Given the publicity someone is probably already planning on looking into it.
Publicity is one of the major differences between crank science that is
ignored and other things like the reactionless drive at NASA.

I wouldn't say that papers are ignored because they must be wrong. It's hard
to make a definitive statement either way, but "revolutionary" experiments
very rarely come with good rigor and examination (the neutrino experiment is
one of the few counterexamples, it was excellent). Crappy papers get ignored,
revolutionary or not. It's very rare that a paper is well-done, upsets normal
beliefs, and isn't immediately seized on by the media and community.

------
nocman
From the article: "Goodenough invented the heart of the battery that is all
but certainly powering the device on which you are reading this."

^ rumors of the demise of the desktop are greatly exaggerated.

Yeah, I get it, a lot of people read internet articles on a tablet or phone,
but using the phrase "all but certainly" is way beyond the scope of reality. A
brief google search suggests mobile usage is probably between the 50% and 60%
of internet traffic.

Yeah I think mobile will continue to grow, but I don't think the desktop will
disappear in the near future, if it ever does completely. Of course, the
blurring of the lines between the two could cause making the distinction to
become more challenging.

~~~
elif
besides the obvious of laptops being a large part of the 40-50% "desktop"
figure you use, the CMOS battery in your desktop tower is lithium.

~~~
YSFEJ4SWJUVU6
CMOS battery does not power a running computer, though.

~~~
elif
Correct. if you never shut down or restart your computer, it is never powered
by lithium batteries, however that niche is consistent with the authors use of
"all but certain"

------
aetherspawn
Title reads like a bad dip.ly clickbait...

