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U. Alberta team developing new high power and energy lithium-carbon battery system using induced fluorination; dual storage mechanism

18 August 2014

Srep05310-f5
Ragone plot, comparing Li-CNT-F batteries with other batteries in terms of weight of cathode materials. The highest energy density for Li-CNT-F batteries, 4,113 Wh kgcarbon−1 is presented as a red star. Cui et al. Click to enlarge.

Researchers at the University of Alberta are developing, and, via their spin-out AdvEn Solutions working to commercialize, a new high power- and -energy density battery system: lithium-carbon-fluorine (Li-C-F). Their system is based on a lithium-carbon battery configuration, but with a different approach.

In a paper in Nature’s open access journal Scientific Reports, the team reported that a rechargeable Li-C-F battery (in this case, a Li-CNT-F battery given their use of carbon nanotubes) demonstrated a maximum discharging capacity of 2174 mAh gcarbon−1 and a specific energy of 4113 Wh kgcarbon−1 with good cycling performance.

Reaching beyond the horizon of LIBs [lithium-ion batteries] requires the exploration of new electrochemistry and/or new materials. The recent popular attempts are Li-sulfur (Li-S) and Li-air (Li-O2) batteries. However, there are some formidable challenges for Li-S and Li-O2 batteries, e.g., dissolution of discharging products, poor cathode electrical conductivity, and large volume expansion upon lithiation.

Li-CFx batteries have the highest energy density among all primary lithium batteries with a theoretical specific energy of 2180 Wh kg(Li+CF)−1. A high capacity of 615 mAh gCFx−1 was also reported for the pre-synthesized CFx cathodes. It is well known that defluorination of carbon fluorides can be achieved with the assistance of lithium cations during discharging in Li-CFx batteries. However, Li-CFx batteries have attracted limited interest because of their strictly non-rechargeable nature and the non-environmental-friendly synthesis process for carbon fluorides, e.g., the use of F2 gas and/or catalysts under extreme temperature conditions.

In a departure from previous approaches, we adopted the lithium-carbon battery configuration. Instead of using carbon materials as the surface provider for lithium-ion adsorption and desorption, we realized induced fluorination of carbon nanotube array (CNTA) paper cathodes, with the source of fluoride ions from electrolytes, by an in-situ electrochemical induction process. The induced fluorination of CNTA papers activates the reversible fluorination/defluorination reactions and lithium-ion storage/release at the CNTA paper cathodes, resulting in a dual-storage mechanism. It is the first time that the reversible fluorination/defluorination reactions were realized at pure carbon and non-fluoride materials. … After the battery cells were assembled, CNTA paper cathodes with no binding materials and no conductive additives were in-situ fluorinated by induction charging for a number of cycles, which enables Li-CNT-F batteries with high energy density and high reversibility.

—Cui et al.

Srep05310-f1
Dual-storage mechanism with reversible fluorination/defluorination reactions and lithium-ion storage/release occurring at CNTA paper cathode.

a) Induced fluorination of CNTA papers occurring during an electrochemical induction process, which also destructs the graphitic carbon structure to defective structures.

(b) Defluorination of the in-situ formed carbon fluorides by the conversion reaction with lithium ions; meanwhile, additional lithium ions store in the defective carbons.

(c) Lithium ions release from the defective carbons; meanwhile, the fluorination of the defective carbons by the reversed conversion reaction in (b). In particular, the LiF metastable solids formed in (b) and facing the electrolyte will be dissociated during charging.

Cui et al. Click to enlarge.

AdvEn Solutions hopes to have a prototype by the end of 2014 and aims to develop three versions of the battery to serve different goals. One battery would have a high power output and a long life cycle, the second would have high energy for quick charging, and the third a super-high energy storage.

AdvEn is a growing company housed within the Department of Chemical and Materials Engineering at the U of A. It aims to expand by taking on new researchers and gaining more funding. The company recently secured a partnership with the US-based aerospace company Lockheed Martin to develop an advanced anode for AdvEn’s high-performance carbon cathode.

Resources

  • Xinwei Cui, Jian Chen, Tianfei Wang & Weixing Chen (2014) “Rechargeable Batteries with High Energy Storage Activated by In-situ Induced Fluorination of Carbon Nanotube Cathode” Scientific Reports 4, Article number: 5310 doi: 10.1038/srep05310

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Comments

It is proving incredibly tough to move beyond the specific energy of the Panasonic batteries used in the Tesla S, and other companies who did not fancy using 18650's have had a hard enough time simply to equal it.

They seem to be managing to catch up now, but there is almost no sign that anyone is anywhere near going beyond it.

Nissan also tells us they lose money on their $270 kwh battery pack and I will not trust Tesla's supposed costings until I see an externally audited report.

The meme of ever onward and upward in batteries seems in serious doubt to me.

Good to know that someone here is holding the line on the contrarian view. With all the good news published on these pages daily, it would be easy to become giddy with optimism.

For my part, I'm more on the realistic view. Some of them will pan out, for certain markets...3-5 years later than these first announcements make us all giddy. LOL

@Davemart

Nissan has also said they're selling the Leaf at a profit (even the base model) as of Nov 2013 so there's a hard limit on how much they're subsidizing that battery pack.

Price drop rates have exceeded every study based prognostication; notice the price keeps dropping as time continues for the studies.

March 2012 study says $397 per kWh for packs by 2020
http://www.greencarcongress.com/2012/03/lux-liion-20120327.html

July 2012 study - packs at $200 per kWh by 2020

http://www.plugincars.com/lithium-ion-battery-prices-drop-160-kwh-2025-123193.html

Nov 2013 study - packs at $180 per kWh by 2020

http://green.autoblog.com/2013/11/08/li-ion-battery-prices-headed--down-180-kwh/

What we need is for battery and car companies to stop hiding information from the public. Tell us what batteries cost. Their competitors almost certainly know.

The batteries are going to come. They're not coming as fast as we'd like, but there are SO many people putting real resources behind this now, that the advances will come.

Davemart, for someone that can be SO positive on everything hydrogen, despite all the hurdles it faces, I am surprised to see you so negative on batteries. All I can say is:

Why don't you knock it off with them negative waves? Why don't you dig how beautiful it is out here? Why don't you say something righteous and hopeful for a change?

I remember many years ago watching the television industry fretting over how long it took to roll out high definition and flat screens. It took far longer than anyone imagined, and the view was that maybe no one cared about better picture quality.

Well it came and it got cheap and who even remembers a CRT anymore? OK, plasma screens are dying, other technologies never made it, LCDs just kept getting better.

What difference does it make if the 18650 cells end up being the long term solution the way LCDs ended up? I think 18650 is improbable, but who cares? Electrification is coming. One way or another. I know my wife will never drive another gas car, it is like smoking cigarettes. No thanks. Can't afford it. On many levels.

According to a new report from Navigant Research, worldwide revenue from next-generation advanced batteries will grow from $182 million in 2014 to more than $9.4 billion in 2023.

http://www.navigantresearch.com/newsroom/next-generation-advanced-batteries-will-reach-9-4-billion-in-annual-revenue-by-2023

Battery technology will soon get out of research labs. Sometime between 2020 and 2025 mass produced lower cost 1000+wh/Kg units will be available for affordable extended range BEVs.

Teslas S160 to S320 and other extended range vehicles will become common place and will progressively replace polluting ICEVs.

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