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Argonne-led team demonstrates Li-air battery based on lithium superoxide; up to 5x Li-ion energy density

19 January 2016

Researchers from Argonne National Laboratory, with colleagues in the US and Korea, have demonstrated a lithium-oxygen battery based on lithium superoxide (LiO2). The work, reported in the journal Nature, could open the way to very high-energy-density batteries based on LiO2 as well as to other possible uses of the compound, such as oxygen storage.

Lithium-air batteries form lithium peroxide (Li2O2)—a solid precipitate that clogs the pores of the electrode and degrades cell performance—as part of the charge−discharge reaction process. This remains a core challenge that needs to be overcome for the viable commercialization of Li-air technology. However, a number of studies of Li–air batteries have found evidence of LiO2 being formed as one component of the discharge product along with lithium peroxide (Li2O2).

Unlike lithium peroxide, lithium superoxide can easily dissociate into lithium and oxygen, leading to high efficiency and good cycle life. In addition, theoretical calculations have indicated that some forms of LiO2 may have a long lifetime.

These studies also suggest that it might be possible to form LiO2 alone for use in a battery. However, solid LiO2 has been difficult to synthesize in pure form because it is thermodynamically unstable with respect to disproportionation, giving Li2O2.

Here we show that crystalline LiO2 can be stabilized in a Li–O2 battery by using a suitable graphene-based cathode. Various characterization techniques reveal no evidence for the presence of Li2O2. A novel templating growth mechanism involving the use of iridium nanoparticles on the cathode surface may be responsible for the growth of crystalline LiO2. Our results demonstrate that the LiO2 formed in the Li–O2 battery is stable enough for the battery to be repeatedly charged and discharged with a very low charge potential (about 3.2 volts).

—Lu et al.

The major advantage of a battery based on lithium superoxide, Argonne battery scientists Larry Curtiss and Khalil Amine explained, is that it allows, at least in theory, for the creation of a lithium-air battery that consists of a closed system. Open systems require the consistent intake of extra oxygen from the environment, while closed systems do not—making them safer and more efficient.

The stabilization of the superoxide phase could lead to developing a new closed battery system based on lithium superoxide, which has the potential of offering truly five times the energy density of lithium ion.

—Khalil Amine

The researchers attributed the growth of the lithium superoxide to the spacing of iridium atoms in the electrode used in the experiment.

However, this is just an intermediate step. We have to learn how to design catalysts to understand exactly what’s involved in lithium-air batteries.

—Jun Lu, lead author

The researchers confirmed the lack of lithium peroxide by using X-ray diffraction provided by the Advanced Photon Source, a DOE Office of Science User Facility located at Argonne. They also received allocations of time on the Mira supercomputer at the Argonne Leadership Computing Facility, which is also a DOE Office of Science User Facility. The researchers also performed some of the work at Argonne’s Center for Nanoscale Materials, which is also a DOE Office of Science User Facility.

This discovery really opens a pathway for the potential development of a new kind of battery. Although a lot more research is needed, the cycle life of the battery is what we were looking for.

—Larry Curtiss

The work was funded by the DOE’s Office of Energy Efficiency and Renewable Energy and Office of Science.


  • Jun Lu, Yun Jung Lee, Xiangyi Luo, Kah Chun Lau, Mohammad Asadi, Hsien-Hau Wang, Scott Brombosz, Jianguo Wen, Dengyun Zhai, Zonghai Chen, Dean J. Miller, Yo Sub Jeong, Jin-Bum Park, Zhigang Zak Fang, Bijandra Kumar, Amin Salehi-Khojin, Yang-Kook Sun, Larry A. Curtiss & Khalil Amine (2016) “A lithium–oxygen battery based on lithium superoxide” Nature doi: 10.1038/nature16484

  • Ujjal Das, Kah Chun Lau, Paul C. Redfern, and Larry A. Curtiss (2014) “Structure and Stability of Lithium Superoxide Clusters and Relevance to Li–O2 Batteries” The Journal of Physical Chemistry Letters 5 (5), 813-819 doi: 10.1021/jz500084e

January 19, 2016 in Batteries, Li-O2 | Permalink | Comments (13)


Could this technology (combined with others) have the potential for future 5X-?X-?X batteries for future extended range BEVs?

It so, can in be done between 2020 and 2025?

suitable graphene-based cathode
Has any group actually mass produced graphene cost effectively?

I got to laugh. This sound like a fantastic thing but in Chicago today it was sub zero again and there are hybrids that wont even RUN when the temp gets this cold. You buy a 40K car and it doesn't run because its too cold?
If they could bring this to market in less than 2 years they may have a chance but looking at the price of gas today, 1.66 a gallon in Chicago the window to make this happen narrows substantially. NO ONE wants to drive a SMALL under powered car. People will buy only buy one if they have to. Thats whats WRONG with all of this tech. Its not based on actual desire of people to drive a small under powered car that doesn't behave when its cold out.
Its why I think hydrogen might make it vs BEV cars.
PEOPLE don't want to pollute but when push comes to shove they do when it hinders their forward progress.
I don't love oil and hoped that the EV revolution would greatly REDUCE the cost of cars but years after the cars have been introduced, and MANY cars have been created, the cost has NOT come down far enough. So you are asking people to buy cars that COST MORE and give you less. Its counter intuitive.

@D Modern electric cars, whether battery electric or plug in hybrid, are definitely not underpowered and most are not small.

Take a look at the latest Volvo - 400hp and 7 passengers. In fact there are now 6 SUVs that are electric, plus the new PHEV minivan from Chrysler. None of those cars have any more problem operating in the cold than any other gas powered car. Which is to say, for a modern car, none south of the Arctic Circle.

There are now a dozen new EVs that can be leased for $200-250 per month. On a monthly total cost of ownership, the cost is substantially less than a gas car.

If you think gas is going to stay cheap forever, you might want to take a look at an historical price chart. The only thing certain is that prices will continue to go up and down over time, like a wave. But over long time periods, the trend is up not down.

Our upcoming edition of the EV Buyers Guide lists 42 electric vehicles for sale in the US. Most are very impressive, especially in comparison to any car a decade or two old.

The Lithium ion peanut gallery should read this:

Maybe they'll think twice about what goes into their favorite cars.

My son and I have Toyota Camry Hybrids and we have no problem (at all) with colder weather than Chicago.

Our Province has only 8,500 BEVs (50% of Canada's) to date but our provincial government claims that we will have 100,000 BEVs in calendar year 2020 or in about 4.5 years. That's a tall order but doable? The current CAN $8,000 subsidy may have to be increased to CAN $10K or $12K.

Nobody knows how many FCEVs will be on our roads by then or if they will be part of the 100,000. I too would prefer a 500+ Km range FCEV over an extended range BEV to face our long cold winters.

So what's with the cold weather - b.s?
The only real world experience I have with it, aside from my next door neighbour recommending it, is a starter battery.

The performance curves from the manufacturer show an increase in amps out as the cranking cycle proceeds and some internal warming occurs. Direct contradictory - so learn me?
It sits for months without loss of bite.
very very happy me.

'parently coal is nearly as cheap as wood - only wish I'd kept my old watt's engine.
At least the hot bulb stratified charge donk in the back shed is still 'right to go'

I think you'll find an adequate answer to your question under this link.

Good, because it sells for $100 per gram at suppliers.

Rocket fuel:

2(LiO2) + 2(H2) = Li2O2 + 2(H2O)

Arnold, try driving at -35C with high winds, snow drifts and slowed traffic. I doubt if you would appreciate the average short range BEV over 30-40 minutes or so before calling a CCA/AAA tow truck.

While waiting, your (essential) feet and hands may freeze beyond repairs.

The only BEVs on our roads during winter months are the TESLA S-85/S-90 (with brave drivers). All others are stored for 4+ months.

Electrified SUVs (or equivalent) with 180+ kWh batteries could be a good compromise.

That may be a growth service, mobile charging trucks.

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