A superion conductive material for sodium based batteries.

[NNadir]

One hears a lot about batteries these days, usually in connection with the unfortunate fantasy that so called "renewable energy" will someday become a significant and clean for of energy; that all our problems will be solved if only we had great batteries to store our wind and solar energy that we imagine is already significant and cheap.

They haven't been; they are not; and they will not be significant and cheap, but no matter. (After 50 years of cheering, solar and wind do not produce 10 of the 576 exajoules humanity generates and consumes each year, as of 2016.)

In any case, I'm not so sure that batteries are a good idea in a purely environmental sense, since they require that humanity generates more energy than it already does:

A battery is a device that wastes energy owing to the second law of thermodynamics, but this said, there are many applications - we all use them - where they are desirable and in fact, essential, a fact that has nothing to do whether the source of electricity is relatively dirty - fossil fuels and to a lesser extent solar and wind - or clean, nuclear energy.

The best batteries in the world of course are currently lithium batteries, but there are reasons that they are not ideal, one being that lithium is an ion that is known to have profound biological effects, primarily neurological, and secondly - although I don't believe that it is as critical an issue - it is somewhat problematic to obtain and refine it.

A better element for economic and environmental reasons would be sodium, since it is readily available in vast quantities, is cheap, and is an essential component of all living things, and thus is non-toxic.

Thus it was interesting to encounter a paper on the path to making sodium batteries, moreover solid state sodium batteries, this paper: Na11Sn2PS12: a new solid state sodium superionic conductor (Nazar et al, Energy Environ. Sci., 2018, 11, 87-93)

In the introduction, the authors review the state of the art in solid phase batteries.

All-solid state batteries (ASSBs) have emerged as very attractive alternatives to conventional liquid electrolyte cells, because of their enhanced safety and higher energy densities.1,2 While development of Li-ion ASSBs is well underway owing to major advances in Li-ion solid state sulfide-based electrolytes that exhibit good ductility,1,3–6 their sodium counterparts lag behind, in part due to a paucity of fast Na-ion conducting analogues.7–9 Amongst the various solid-state electrolytes that have considered for solid state Li-ion systems, the remarkably high ion conductivity of Li10GeP2S12 (“LGPS”, 12 mS cm?1) reported in 2011,3 has inspired growing interest in sulfide based ion-conductors and especially in lithium thiophosphates.4–6 These materials generally exhibit high conductivity and their ductile nature makes them relatively easy to process.4–6 While the aim is to obtain glass-ceramic compositions that can optimize or eliminate grain boundaries, a fundamental understanding of ion conduction in these materials must be founded in studies of single-phase crystalline materials,10 invaluable theoretical studies6,11 and/or studies of ion dynamics.5 Several substitutions in the LGPS family have been explored successfully using Sn4+, and Si4+ to replace (partially or completely)12–19 expensive and reducible Ge4+. Oxygen has partially replaced sulfur, thus potentially increasing the stability towards moisture, however this has been shown to lower the ion conductivity.20

Germanium, Ge, is an element that is readily subject to depletion, even if lithium resources can be extended nearly indefinitely, at least in the case where one has sufficient energy to isolate it.

The authors then report an alternative, the sodium tin phosphorous sulfide battery which can be manufactured from earth abundant elements, as opposed to lithium and germanium.

Here is the (beautiful) structure of their sodium ion conducting material:



Here's the caption of the diagram:

Fig. 1 Structure of Na11Sn2PS12 from single crystal data. (a) The framework showing ordering of the SnS4 (dark blue) and PS4 (light blue) tetrahedra; yellow spheres are S; and rose/red ellipsoids are Na ions. The Na(1)/Na(2) ions (sites with fractional occupancy) are represented by rose ellipsoids and the Na(3)/Na(4)/Na(5) ions (almost fully occupied sites) are shown as red ellipsoids. (b) The small tetragonal cell (a? × a? × c? equivalent to Li10GeP2S12 is related to the actual tetragonal cell (a × a × c) of Na11Sn2PS12 as follows: a = a?√2; c = 2c?; (c and d) views of the ab planes consisting of interconnected NaS6 octahedra shown in red (Na(3)/(4)/(5)) and rose (partially occupied Na(1)/(2)); (e) view of the Na(4)–Na(1)–Na(3)–Na(1) chains that run along c. All five Na+–Na+ distances are close to 3.4 Å, making hops between the sites virtually equipotential.

There's some nice details on the synthesis of their ion conductor as well as measurements of its ion conductive properties, etc, and then some nice discussion of modeling of the structure via DFT (Density Functional Theory) calculations.

It's interesting and cool I think. I personally believe that sodium based batteries are a better idea than lithium batteries, but that's just my opinion.

Have a nice weekend.

[Wellstone ruled]

1. Now,if they can get this product to

a commercially viable use. Lithium has a toxic waste factor which will never go away. And there are only a few known sources that can be commercially viable. And the unknown is,what is happening as the Water evaporates? Been to the Silver Peak Facility here in Nevada,the prevailing down slope winds in the area carry the dust several miles east of this Pump site.

Any alternative will win the day.

[mr_lebowski]

2. I know you love your Nuke Power and all, but calling it 'clean' is a stretch ...

Yes, it's relatively clean ATMOSPHERICALLY ... but terrestrially?

Let's just say I'm not sure how you consider generating many 1000's of tons of what is basically the absolutely MOST TOXIC WASTE known to friggin' man ... to be a 'clean' process.

Uranium Mining ain't exactly 'clean' either.

Then there's the dangers of transporting the materials, chances of it falling into the hands of terrorists, chances of mass deaths due to meltdowns, etc, etc, etc.

I think it has a valid spot in the 'mix' but it's not really any MORE of a true panacea than the 'renewables' that you like to laugh about if one is honest to oneself about it.

JHMO, YMMV.

Thanks for sharing about the batteries though. Like you, in general, not a huge fan of 'batteries' being used for large-scale power storage. As you've correctly pointed out elsewhere, pumped hydro makes a whole lot more sense where possible.

One thing I've long wondered ... is there ANY chance we someday might be able to overcome (or at least greatly reduce) the significant energy loss over distance that occurs with our current power transportation systems? Or is that just one of the 'physically impossible' problems like building a perpetual motion?

Cause it seems to me that if it could somehow be greatly reduced, it might at some point become practical to set up, say, 12 HUGE interconnected solar generation sites around the world in strategic locales. Logically, they'd be roughly in the equatorial region, and roughly 'evenly spaced', such that the Sun is always shining on a handful of them ... then we wouldn't necessarily 'need' batteries (though we might still want some local generational ability of various kinds just in case), cause the world would have an 'always on' source of power.

[NNadir]

3. The high energy to mass ratio makes nuclear much cleaner than all alternatives.

Last edited Sun Jan 21, 2018, 01:12 PM - Edit history (2)

It is, in my view, the cleanest form of energy possible.

You seem to think that used nuclear fuel is unique in accumulating "1000's of tons: of what you call "waste." Have you stopped to consider that dangerous fossil fuels produce millions of tons of waste every damned day?

Used nuclear fuel is actually vastly superior to all other forms of energy on this score, in particular because much of what you call "waste" consists of insoluble materials, as contrasted with the gaseous waste - 35 billion tons a year - produced by fossil fuels.

Your statement that the material in used nuclear fuel is the "MOST toxic waste known to man" is also nonsensical and absurd.

I would note that the microcystin formed in Lake Erie in 2012, because people propose the absurd notion that dangerous fossil fuel waste, specifically nitrates and climate forcing gases, is extremely toxic. A few micrograms of some forms of microcystin can kill a man in minutes, and yet it was being formed rapidly in Lake Erie.

Of course, nobody gives a shit if people die from climate driven microcystins, but they're all over allegedly "MOST toxic nuclear 'waste'.

Which is easier to control, 75,000 tons accumulated over half a century in the United States of used nuclear fuel with an average density of around 15 - 18 grams per ml or all of Lake Erie?

All of the nuclear fuel, the majority of which consists of naturally occurring uranium (about 95%) could be easily stacked on a football field.

Lake Erie? The planetary atmosphere? The oceans. You do realize that the oceans naturally contain about 5 billion tons of uranium, or do you?

I wish that the same people who complain - and frankly ignorantly - would consider if this allegedly "MOST toxic waste" could present any evidence that in half a century all of it accumulated over all time has killed as many people as will die in the next 5 hours from air pollution.

What does "dangerous" mean to people who can't do this simple - extremely simple - comparison?

I would submit that the word "dangerous" implies that it actually harms people, like for instance, dangerous fossil fuel waste, aka "air pollution" that kills seven million people per year from the normal operations of dangerous fossil fuel plants, even without invoking climate change which is both real and serious.

What do you personally know about the components of used nuclear fuel that allows you to make such an assertion that it's "dangerous" and most toxic.?

The Bateman equation dictates - and this is a law of mathematical physics and not some made up garbage thinking on an anti-nuke website - that there is an absolute maximum to the amount of radioactive materials can accumulate before they are decaying as fast as they are formed. This amount is never actually reached, it's approached asymptotically. It can be shown by solution of one of the simple forms of this differential equation that the amount of nuclear energy being generated right now rounded slightly up to 30 exajoules per year, (as of 2016 nuclear power plants were producing 28 exajoules per year) that the maximal amount of cesium-137 that can accumulate is roughly 610 metric tons. During the first year of operations on 30 exajoules of new plants would accumulate a little over 14 tons per year of new Cs-137, but since it decays proportionately to the amount accumulated, new Cs-137 would be accumulating at a rate of 4.5 tons a year in the 50th year and roughly 1.4 tons per year in the 100th year.

(I'm pulling this data off a spreadsheet I built after solving this differential equation and noting that cesium-137 has a very low neutron capture cross section as well as a high yield in fission)

Cesium can easily be made into insoluble cesium titanate and utilized to destroy atmospheric and aqueous powerful organohalide carcinogens.

This garbage about "nuclear terrorism" is also delusional. The nuclear industry is half a century old. Which kinds of terrorists have killed more people, these "nuclear terrorist" boogeymen that people who don't understand shit from shinola about nuclear materials are always prattling on about, or petroleum based fuels diverted to terrorist activities. Ever hear of Oklahoma City or the World Trade Center?

Either one of two cases is possible. Either nuclear materials are too dangerous to handle and therefore inaccessible to boogeymen "terrorists" or its easy to handle and therefore as accessible to terrorists as fertilizer was for Timothy McVeigh to handle.

Which is it?

Your selective attention is frankly toxic, since it is intended to demonize which experimentally has been proven to have the lowest death toll per decade of any form of energy utilized by humanity that has successfully produced more than 10 exajoules of energy per year for a period of more than 3 decades.

I would submit to you also that you seem to know very, very, very, very, very little about the toxicology associated with solar materials, which are neither sustainable, non-toxic or available in unlimited supply.

Do you know what the latest fad in solar research is, all over the scientific literature in what I find to be a highly questionable search for the solar chimera that never comes?

Here, let me tell you with a paper I scanned through this afternoon:


A Mechanistic Study of Phase Transformation in Perovskite Nanocrystals Driven by Ligand Passivation (Kazes, et al Chem. Mater., 2018, 30 (1), pp 84–93)

I wish I could say that this was the only paper I read on these halide perovskites today, but I would be kidding myself.

And do you know what these "highly efficient perovskite solar cells" that have "revolutionized solar research" are made of?

They're made of lead, cesium and iodine, the formula for the most common perovskite being investigated for the "solar revolution" that people imagine will be "green and clean."

Bullshit. I am personally opposed to spreading lead over hundreds of thousands of hectares of pristine land because people have fantasies about the solar revolution. I'm aware of lead paint and what it did - distributed lead - and lead gasoline and what it did (still being aerosolized whenever California catches fire which with climate change, it's doing a lot.).

Now enslaved to the unthinking rote notion that distributed energy is "green" we are researching how to distribute more lead for crap that will be electronic waste in 30 years of less? Millions upon millions of tons of it.

I'm an old man. I'm going to die soon enough. I am disgusted, absolutely disgusted, that in my long and beautiful lifetime we haven't seemed to have learned a damned thing about what is and what is not environmentalism.

The key to clean energy is energy to mass data. No system of energy approaches nuclear energy on that score. The demonization of nuclear energy and the myths that surround it in the popular mentality is more toxic than all of the nuclear accidents that have ever happened, Chernobyl, Fukushima, blah, blah, blah ad nauseum.

Combined, all of the nuclear accidents throughout the entire history of nuclear energy have not killed as many people as will die in the next two days from fossil fuel waste - waste that continues to be dumped because people lie around all day picking lint out of their navels and contemplating the grand so called "renewable nirvana" that never comes.

Rather than do this, it would be useful to open science books.

Regrettably that never happens.

Nuclear energy is not perfect. It is not without risks. But it doesn't need to be to be vastly superior to everything else, which it is.

Oh, and about uranium mining. I oppose it. The uranium already mined as well as the radioactive thorium by product of the lanthanides mined to create the stupid wind industry, when fed into fast reactors is sufficient to provide all the energy humanity consumes for the next two or three centuries.

If humanity survives - and it may not because of stupidity and selective attention with respect to environmental issues - one hopes that future generations, the generations we screwed, will be smarter than we are.

Because while we sit around fearing "terrorists" who don't, in fact, exist, the planet is actually dying.

Have a pleasant Sunday.

[mr_lebowski]

4. Wow, touchy ... you make a lot assumptions about what I know and don't ...

And a lot of assumptions about what broad swathes of the population know/believe as well.

I've told you twice now on different threads that I'm really not 'anti-nuke'. I don't read anti-nuke sites. I have a BS in Environmental Sciences, and have a very close relative who's worked at one of our NPP's for ... 35 years now I wanna say? He's about to retire, but staying to oversee the decommissioning. His wife works there as well.

Seems you've elected to use ME as a punching bag/stand-in for all people you disagree with when it comes to nukes ... when in reality, I do not disagree with MOST of what I've seen you arguing.

I harbor no illusions that it's in any way 'likely' that 'solar' and/or 'wind' and/or 'geothermal' or whatever you might name ... is currently a panacea. I think many people, as you've stated, are not thinking at nearly as sophisticated a level when it comes to so-called 'renewables' ... as they should be. Many have in fact been 'sold a bill of goods' and don't bother understanding the 'downsides', or refusing to admit to them ... if they do. Our opinions on this are not that far off.

However, I also don't discount the possibility that SOME form of solar power capture (who knows, maybe algae farms will end up making a ton of sense, and the 'panels' will end up retired as a concept ... I dunno) might not eventually be a very logical choice to provide significant amounts of humanities energy. As a source, it's FREE (as is wind), given that the sun is striking the earth every day anyway (thank Dog) so its really an OPTIMAL SOURCE of power, if we can indeed suss out for ourselves a way to make it 'useful' for electricity generation ... in a reasonably clean way.

ATM, in the grand scheme of things, it's not at all debatable that per joule generated, nuclear power is the 'cleanest' form of energy apart from hydro. I'd never in 1M years try to claim that nuclear is dirtier than ANY fossil fuel, so not sure what THAT whole rant was about ... I'd much prefer nuclear over fossil fuel power let me be very clear on that.

It's very unfortunate and short-sighted that today's economic 'climate', if you will, fails to account for the way that the fossil fuel industry is 'socializing' the 'health costs' of their business, while 'privatizing' their profits.

Whereas nuclear power in our current climate is much more difficult to get 'funded', in part because of a semi-unreasonable public worried about accidents, but also in part because of the assc'd insurance costs with building new plants.

And that's because if there were a big meltdown, the deaths that could occur likely would be DIRECTLY attributable to the accident, and would result in a sudden, and scary type of death via acute radiation poisoning.

Whereas a coal-fired plant can belch out toxins for decades, slowly poisoning everyone downwind ... but nobody who this plant has hastened the demise of ... can ever prove that the plant was 'at fault', ergo, its operators don't need nearly as costly of insurance relative to a nuclear facility. Nor is anyone as acutely 'scared' of a Coal plant ... since it'll just kill ya slowly, not suddenly.

This is definitely one of MANY faults with our Capitalist system ... short-sightedness, and grossly distorted values when it comes to long-term sustainability ... and these traits of it have led to society favoring fossil fuels over nuclear for power gen, despite the many relative disadvantages they actually have.

Enjoy your Sunday as well