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Black phosphorus as high-capacity anode material for Li-ion batteries with strong cycling performance

24 June 2012

Sun
The discharge-charge capacity profiles of black P derived from red phosphorus from 0-2 V (vs. Li+/Li). Dotted line shows theoretical capacity of graphite. The inset shows discharge-charge profiles for later cycles. Credit: ACS, un et al.Click to enlarge.

Researchers from Northeast Normal University, Changchun, China, report that black phosphorus (black P) anode materials for lithium-ion batteries exhibit high specific capacity and excellent cycling performance. A paper on their work is published in the ACS Journal of Physical Chemistry C.

Black P can intercalate three Li ions in the fully discharged state (Li3P) and therefore possesses a high theoretical specific capacity of 2,596 mAh g-1 upon lithiation. This renders black P a potential anode material for Li-ion batteries with high gravimetric and volumetric energy density, the authors noted.

Black phosphorus obtained from white phosphorus at 4 GPa and 400 °C exhibited the highest first discharge and charge capacities of 2,505 and 1,354 mAh g-1. Black phosphorus obtained from red phosphorus at 4.5 GPa and 800 °C exhibited the highest first discharge and charge capacities of 2,649 and 1,425 mAh g-1.

Here we synthesized black P by a high pressure and high temperature (HPHT) method using white and red P separately as starting materials.

—Sun et al.

The team prepared orthorhombic black P using a HPHT method in a cubic anvil high-pressure apparatus under pressures of 2-5.0 GPa and temperatures of 200-800 °C for 15 min. For electrochemical measurements, they used CR2025-type coin cells with metallic lithium as the counter electrode and an electrolyte comprising 1 M LiPF6 in a 1:1 volume fraction of ethylene carbonate (EC) and diethyl carbonate (DEC). Celgard 2400 was used as separator. The working electrode consisted of 80 wt % black P with acetylene black (5 wt %) and polyvinylidene fluoride (15 wt %) in N-methyl-2-pyrrolidone.

During testing, they found that the samples showed large irreversible capacities in the first discharge-charge cycle and initial low Coulombic efficiency. However, after the fifth cycle, the Coulombic efficiency is greater than 95%.

WBP [black P from white phosphorus] and RBP [black P from red phosphorus] samples all exhibited much higher electrochemical activity towards Li insertion than black P samples prepared by HEMM. Although the reaction conditions involved high pressure and temperature, the entire synthetic procedure is simple and rapid. The synthetic conditions can be accurately controlled by regulating the parameters of the high-pressure apparatus.

The highest initial charge capacity of RBP is approximately 3.8 times higher than the theoretical specific capacity of graphite. RBP retained a highly stable capacity of 703 mAh g-1 after 60 cycles, which makes it a promising anode material for high energy Li-ion batteries. These favorable results are attributed to the high crystallinity and purity of the as-prepared black P by HPHT, which may improve the dynamic mechanism of Li ion intercalation/ deintercalation.

Further investigations on black P to improve its overall electrochemical performance (capacity, cyclability, Coulombic efficiency, and voltage profile) will be carried out, including the electrode structure design, controlling cutoff potential, the electrolyte choice and the surface coating treatment etc. These results will be reported in a future publication.

—Sun et al.

Resources

  • Li-Qun Sun, Ming-Juan Li, Kai Sun, Shi-Hua Yu, Rong-Shun Wang, and Hai-Ming Xie (2012) Electrochemical Activity of Black Phosphorus as an Anode Material for Lithium Ion Batteries. The Journal of Physical Chemistry C doi: 10.1021/jp302265n

June 24, 2012 in Batteries | Permalink | Comments (9) | TrackBack (0)

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Comments

I assume/hope many of these hundreds of arcane advances are providing the multiple avenues for much better batteries that one would assume.

At least as many as new technologies are offering ICEs.

@ Toppa Tom. These studies\experiments are not hundreds of arcane advances. These are just false reports made of non-senses. They have to make reports because it's their jobs, they are paid by big oil to retard any real progress. They, big oil, know exactly how to get energy at low cost without pollution but they are not interrested a single second to know it except if it's to make a patents about it to prevent anybody of using it and commercialise it. They know that hydrogen gas and hydrogen fuelcells are the hot thing, they made tons of patents about it years ago and they are not interrested to commercialise it. So now after made the car manufacturers and obama and bush postponing hydrogen endlessly, they just have to entertain the crowd about useless batteries with false reports. They never gonna invent a battery that is better then the current batteries that are actually very costly and very limp. Tesla is an employee of big oil and banks and they invest a part of their profits in battery related public relation brainwash to cover the entire operation that is to sell as much petrol as possible at the highest cost destroying the car market and the economy and internationnal peace economy and wars.

You are then one of them been paid somewhere or you are a victim of the brainwash. Why wait for a miracle while hydrogen have been proven non-polluting and wear free and cheap and completly sustainable and there is an infinite number of methods to produce hydrogen cheaply in endless quantity.

Few are interrested to commercialise hydrogen if they can make more money for themself by doing something else then the right thing like for exemple this false study paid in advance for results known in advance. This study come from workers in china that have just a medium salary, they had to do it just to keep their job and they found nothing, exactly nothing of value and you will never pocess a miracle battery because it's just pr to keep petrol sales alive.

Interesting, but since it's an anode material, it could increase battery capacity only about 10-20%. It's also hard to imagine it will improve what Envia's silicon-carbon composite anodes will do.

This could be one more important step toward future higher performance batteries. Even 20% is important.

When cycled against anything other than the intended cathode material, the cycling data really only suggests potential energy density. Making a full cell is another story though, and takes much more work. The results here are not spectacular, but does suggest an alternative improved anode material for Li ion cells. This could be useful if Si get tied up by patent issues.

There isn't enough phosphor to make this a practical EV battery.

Phosphorus is the 11th or 12th most abundant in the Earth's crust, is it not?

Better start boiling up that urine now...

Ignoring my little quip about urine and considering the importance of phosphorus in fertiliser, I think other types of anode would probably be preferable to this.

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