June 1, 2015

Li-S or Lithium Sulfer Batteries (LSBs) for Submarine On the Way

Energy density diagram comparing batteries including Lead Acid (LABs), Lithium-ion (LIBs) and Li-S or Lithium Sulfer (LSBs)  in watt-hour per kilogram (Wh/kg) and watt-hour per litre (Wh/l). LSBs are projected to be superior. (Diagram courtesy Oxis Energy)

In late May 2015  “S” and I discussed Lithium Sulphur Batteries (LSBs) in the Comments section.
Currently diesel-electric operate using Lead-acid Batteries (LABs). From the 2020s some new-build submarines (including Soryu Mark 2s (28SS) will be utilising Lithium-ionBatteries (LIBs). If HDW 216 or Conventional Barracuda are ever built Australia is probably expecting them to have LIBs.

So Japan has decided to adopt LIBs for the next batch of Soryus the “Mark 2s” (first named here on November 5, 2014 :-). LSBs are intended to have a higher energy density than LIBs or, of course, LABs. However the reliability and safety of all battery types in submarines are essential traits. S advises that GS Yuasa Corporation will be the LIBs supplier for the Soryu Mark 2 which will deliver the LIB sample by 2020. I think this may delay the launch of the first Soryu Mark 2 (28SS) until 2021?

So LIBs may be the new in-operation batteries for submarine from the 2020s while LSBs may be the next advance in batteries for use from the 2030s.

Submarine generational turnover is less a problem in subs for the Japanese Navy (continuous build, one per year with 20 year operating life) than it is in the Australian Navy (non-continuous build, batches of 6 to 12? 30 year operating life).

For Australia it will be a major issue whether retrofitting LSBs in subs already fitted with LIBs will be a practical option. If a sub's whole electrical system (wiring etc) needs to be upgraded then LSBs might need to await the next generation of new-build submarines (2050s on). Australia may be more interested in nuclear propulsion by that time.

If upgrading with LSBs in the 2040s? after 15 years? is considered advantageous by Australia this may perhaps be done during "deep maintenance" when the hull is cut anyway - to replace major engine components.

Probably no-one knows how many years LIBs for submarine will remain efficient. Hence decisions on LSB replacement are far in the future.

Several companies worldwide are researching-developing LSBs. This includes UK company Oxis Energy Ltd. Oxis has provided the diagram above and the description below http://www.oxisenergy.com/technology/ which explains:

"Sulfur represents a natural cathode partner for metallic Li and, in contrast with conventional lithium-ion cells, the chemicals processes include dissolution from the anode surface during discharge and reverse lithium plating to the anode while charging. As a consequence, Lithium-Sulfur allows for a theoretical specific energy in excess of 2700Wh/kg, which is nearly 5 times higher than that of Li-ion.

Oxis’s next generation lithium technology platform offers the highest energy density among lithium chemistry:

-  300 Wh/kg achieved at cell level in 2014
-  400 Wh/kg forecast in 2016

Oxis patented chemistry provides inherent safety allowing it to meet international standards concerning shock, crush, thermal stability and short circuit...Thanks to its two key mechanisms, a ceramic lithium sulfide passivation layer and a non-flammable electrolyte, our cells can withstand extreme abuse situations such as bullet and nail penetrations with no adverse reaction."

Naturally companies need to sell their product and many details need to be worked out with new technologies.

For submarine use batteries need to be very safe (under normal and abnormal conditions) and reliable. Other issues under Australia mission conditions are their:

-  weight
-  charge speed to minimise indiscretion
-  rate of self-discharging
-  memory effect
-  propensity to surge
-  discharge rates (speed, volume, percentage)
-  cycle life and operational life 
-  degree of maintenance needed

It would be interesting which German, French and US companies are developing LSBs?



Anonymous said...

Dear Pete,

as long as there is no commercial usage Lithium Sulfur Batteries (LSB) are far to expensive and unreliable. When I have one in the back of my laptop we can expect them to be on a submarine in the next 10 to 20 years.

400 Wh/kg or 1.44 MJ/kg is still far away from Diesel at 42 MJ/kg but 2,700 Wh/kg or 9.7 MJ/kg is close to the 20 MJ/kg of Methanol.

An all electric submarines could be possible but how do you reload it? Diesel is available nearly everywhere in the world. For long range submarines good LSBs and diesel together make sense.

Research institute: http://www.fem-online.de/en


Peter Coates said...

Hi MHalblaub

Thanks for the info. Of course LSBs would work with diesels rather than instead of diesels. I see the main comparisison for LSBs as being against LIBs and LABs. Yes LSBs are a technology 10-20 years out - for the 2030s as I indicated.

Thanks for http://www.fem-online.de/en - I located within it http://www.fem-online.de/en/content/life-wire-battery-technologies-tomorrow with important last sentence :

"The focus was still relatively young technology of lithium-sulfur batteries. Sulfur lends itself to, is because the material readily available and relatively inexpensive, and has a very high energy density. The first prototypes have already been tested successfully by the mass production, however, the technology is still far away. Is too small to date to exploit the high energy potential, too high capacity loss during use, presented Sörgel firmly. She is currently pursuing different approaches, the first results are very promising. A serious alternative to current lithium-ion batteries will be the sulfur-based system but probably only in about ten years."



Anonymous said...

I wonder which type of LIB will show up in submarines since under the banner of LIB fall under many types. The stuff in our computers are Lithium cobalt oxide. Lithium iron phosphate, Lithium manganese oxide, Lithium nickel manganese cobalt oxide are more damage tolerant but heavier. Lithium nickel colbalt aluminum oxide and lithium titanate are showing up in grid storage and cars. I am guessing it will be the last sub type.
In any case, there is some non trivial design issues with over voltage, over current, under voltage and over temperature. And as the fiasco with the Boeing 787 shows, even the battery box design to contain LIB is a complex job.

Vigilis said...

Hi Pete,

Regarding U.S. manufacturers of Li-S batteries (from 2007):

"SION Power’s lithium sulfur (Li-S) battery, with the highest specific energy of any
rechargeable battery available, enabled QinetiQ’s battery/solar powered Zephyr 6.1 High Altitude, Long Endurance unmanned aerial vehicle(UAV) to beat the official world record for the longest duration unmanned flight. ...At ~10 kg, the Li-S battery pack was carefully engineered to minimize total pack weight."

Although weight (about the density of water) was an overriding limitation in the Zephyr flight, a submarine's confined space environment dictates due care in the use of noxious or potentially hazardous materials. According to advice in a 2005 product safety data sheet (from France's SAFT), Accidental Release Measures: "Remove personnel from area until fumes dissipate".

Is this yet somewhat of a disincentive for submarine usage?

Another interesting topic, Pete.



Peter Coates said...

Hi Anonymous (June 2 at 2:46 AM)

Yes finding the LIB type which is the best balance of energy density, safety, reliability and other qualities, is probably taxing the best minds of all the SSK building countries.

At least LIBs in submarines can be much heavier than those in 787s, thus less prone to heat up quickly and burn. Even fire retardent gas could be pumped into submarine LIB areas.



Peter Coates said...

Thanks Vigilis

Current LSBs still have a ways to go to resolve cycling-operating life and safety issues. Hence it may be the 2030s before they're ready for submarine service.

Though by 2014 some people appeared happy with UAV use http://www.businesswire.com/news/home/20140922005174/en/Sion-Power%E2%80%99s-Lithium-Sulfur-Batteries-Power-High-Altitude#.VWzois-qqko :

"“The performance of the Sion Li-S battery was excellent and the Zephyr was able to exploit the full capacity of the battery due to the high reliability and consistency of the cells, essential for this winter flight. Sion's Li-S batteries are an enabling technology for the Zephyr program..."

Yes LSBs are nowhere near ready for submarine use:

I also had a look at https://in-situ.com/wp-content/uploads/2014/11/Lithium-Thionyl-Chloride-Single-Multi-Cell-Battery-Packs-0048280.pdf :

Page 2

"5. Fire Fiighting Measures
CO2 extinguishers or, even preferably, copious quantities of water or water-based foam, can be used to cool down burning Li-SOCl2 cells and batteries, as long as the extent of the fire has not progressed to the point that the lithium metal they contain is exposed (marked by deep red flames).
Do not use for this purpose sand, dry powder or soda ash, graphite powder or fire blankets.
Use only metal (Class D) extinguishers on raw lithium. Extinguishing media Use water or CO2 on burning Li-SOCl2 cells or batteries and class D fire extinguishing agent only on raw lithium.

6. Accidental Release Measures
Remove personnel from area until fumes dissipate. Do not breathe vapours or touch liquid with bare hands. If the skin has come into contact with the electrolyte, it should be washed thoroughly with water. Sand or earth should be used to absorb any exuded material. Seal leaking battery and contaminated absorbent material in plastic bag and dispose of as Special Waste in accordance with local regulations."

All pretty dangerous for a good while.