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Argonne researchers advancing new class of selenium sulfide composite cathodes that could boost Li-ion energy density 5x

4 December 2013

Master.img-001
Cycle performance of Li cells with (a, b) Se−, (c, d) SeS2−, and (e, f) SeS7−carbon composite as cathodes in ether-based electrolyte. Credit: ACS, Cui et al. Click to enlarge.

New composite materials based on selenium (Se) sulfides used as the cathode in a rechargeable lithium-ion battery could increase Li-ion density five times, according to research carried out at the US Department of Energy’s Advanced Photon Source at Argonne National Laboratory. The work most recently reported in the Journal of the American Chemical Society by a team of researchers from Argonne and King Abdulaziz University (Saudi Arabia) advances their earlier work with selenium as a high energy density cathode material. (Earlier post.)

The researchers have focused on carbon-selenium sulfide composites as an alternative material to the conventional lithium transition metal oxide positive electrode material in standard Li-ion batteries. The new SeSx cathodes could also provide a way around the cycling challenges facing Li-air and Li-S, while delivering a comparable boost in energy density (and hence, for example, range in an electric vehicle.)

State-of-the-art rechargeable batteries are mainly based on conventional lithium intercalation chemistry, using lithium transition metal oxides as cathode material with typical capacities of 120−160 mA·h/g-1. The low energy density and/or high cost of these cathode materials have limited their large-scale production and application in Li ion batteries. Discovery of new cathode materials with higher energy density is, thus, a key to realizing more efficient energy storage systems. Recently, lithium−sulfur (Li/S) and lithium−oxygen (Li/O2) cells have been demonstrated to possess the potential to provide 2−5 times the energy density of conventional Li ion cells. However, both Li/S and Li/O2 cells suffer from poor cycling performance, which had impeded their commercial utilization.

For instance, the cyclability of Li/O2 cells is limited by severe electrolyte decomposition and large cell polarization under deep discharge/charge conditions, while Li/S cells suffer from the solubility of intermediate lithium polysulfide species during cycling, which causes the so-called redox shuttle effect and, thus, poor cyclability.

—Cui et al.

Selenium has higher electrical conductivity compared to sulfur and high theoretical gravimetric capacity (678 mA·h g-1) and volumetric capacity (3,268 mA·h/cm3). In their 2012 paper they we reported that Se represented an attractive cathode material for not only rechargeable lithium ion batteries but also sodium batteries.

There are fundamental issues with the use of selenium that need to be clarified, they noted. For example, they said:

  • Charge and discharge voltages are evolving in the Li/Se system during the initial cycles in the carbonate-based electrolyte. Significant polarization occurs once the charge and discharge voltages are stabilized after five cycles, which leads to a low roundtrip efficiency.

  • The Coulombic efficiency is quite low during the first 20 cycles. The mechanisms or underlying reasons for this unsatisfactory performance are still not well understood due to inadequate characterization of the battery materials during electrochemical cycling.

  • The effects of organic electrolytes on the (de)lithiation process (i.e., both lithiation and delithiation) of the Li/SeSx cells, if any, are still not clear, nor are the effects of the sulfur content in SeSx.

In the study, they adopted an ether-based electrolyte in the Li/SeSx cell to investigate its effect; results showed significantly improved cell performance in terms of voltage profile and Coulombic efficiency.

The voltage profiles of these cells indicate that complete lithiation of selenium to Li2Se is occurring through the formation of intermediate phases, i.e., Li2Sen. This behavior differs from the single-phase transition in carbonate-based electrolyte, as reported earlier. This result clearly suggests that cell performance highly depends on the nature of the electrolyte.

—Cui et al.

To examine electrochemical performance in the ether-based electrolyte, they tested active cathode materials containing Se, SeS2, and SeS7 combined with carbon against Li metal anodes between 0.8 and 4.0 V. A discharge capacity of 350, 571, and 833 mA·h g-1 for the Li/Se, Li/SeS2, and Li/SeS7 cells, respectively, was maintained for more than 50 cycles.

Capacity increased with increasing S content in the composites due to its contribution to the overall capacity. The capacity faded a little for all three cells tested. The Coulombic efficiency was nearly 100% for the Li/Se and Li/ SeS2 cells. The Li/SeS7 cell showed a relatively low Coulombic during the initial 20 cycles, although much higher capacity.

Using the X-ray Science Division (XSD) beamline 11-ID-C at the Advanced Photon Source, the team carried out in situ synchrotron high-energy x-ray diffraction (HEXRD) studies and complementary, selenium K-edge x-ray absorption near-edge structure (XANES) analysis to observe the chemical changes that take place in these novel electrode materials as they charge and discharge a battery.

These measurements, which were undertaken at more than 12-keV energy, were also done in transmission mode on the XSD bending-magnet beamlines 9-BM-C and 20-BM-B. This technique allowed the team to hone in on the changing chemistry of the selenium atoms in the electrode and how they shift between crystalline and non-crystalline phases as current and lithium ions flow through the experimental battery’s ether-based electrolyte. Raman microscopy at Argonne’s Center for Nanoscale Materials provided additional information about the Li2Se that was observed on the Li anode of the charged cells.

The team discovered that it is the chemical composition of the electrolyte that seems to have the most impact on the changes that take place. The researchers suggest it might be possible to tune the efficiency of a battery based on these new composites by optimizing the electrolyte and so improve battery performance still further.

The x-ray studies and analysis of the electrochemistry of the electrode as it operates also allowed the team to suggest a plausible chemical mechanism for the processes involved in discharging the battery.

The composite electrode is reduced to form lithium polyselenide with more than four selenium atoms per lithium atom; additional discharging to lower voltage leads to chemical species containing two lithium ions per selenium atom. Charging involves the reverse process. This mechanism is first proposed and experimentally proven by the team, and it is similar to that seen in experimental lithium-sulfur electrodes.

Resources

  • Yanjie Cui, Ali Abouimrane, Jun Lu, Trudy Bolin, Yang Ren, Wei Weng, Chengjun Sun, Victor A. Maroni, Steve M. Heald, and Khalil Amine (2013) “(De)Lithiation Mechanism of Li/SeSx (x = 0−7) Batteries Determined by in situ Synchrotron X‑ray Diffraction and X‑ray Absorption Spectroscopy,” J. Am. Chem. Soc. 135, 8047 doi: 10.1021/ja402597g

  • Ali Abouimrane, Damien Dambournet, Karena W. Chapman, Peter J. Chupas, Wei Weng, and Khalil Amine (2012) “A New Class of Lithium and Sodium Rechargeable Batteries Based on Selenium and Selenium–Sulfur as a Positive Electrode,” J. Am. Chem. Soc. doi: 10.1021/ja211766q

December 4, 2013 in Batteries | Permalink | Comments (9) | TrackBack (0)

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Selenium is rare element, we only produce 2000tons a year, so good research but little future except for some military or high tech use

Another potential variance towards improved 600 to 1000 Wh/Kg future batteries.

Many new battery technologies will come out of Research Labs by 2020 or so.

Improved (5X) batteries could generate EVs with 500+ miles range.

Those extra long range BEVs may require 200+ KW charging facilities on major highways. It would not be an impossible challenge, but overnight charging could be done with 10X to 12X less or at under 20 KW during 10 to 12 hours.

The Fed Battery hub is budgeted for 5X, 1/5th cost, in five years - so EV battery performance should more than double this second hub year.

It seems that there are multi-fold improvements announced for ONE battery component - that never was compatible with other improved components

"Selenium is rare element, we only produce 2000tons a year, so good research but little future except for some military or high tech use."

It can not be that rare as selenium sulfide is a commonly used ingredient in medicated hair shampoo. You can buy 1% strength over-the-counter (Head and Shoulders in dark blue container) or 2.5% with a prescription. Look for it next time you are in a drug store.

At 5x the range for an equal cost i might be interrested to buy a pure bev if it's proven than a fast charge do not tear apart a battery faster then a slow charge. I park in the street and do not do a lot of mileage. I know a guy that do 140 miles a day in a nissan xterra each day to go to work in heavy traffic, some are crazy but with this battery he would be a little less crazy. He should be interrested to buy, probably, i will talk to him about this battery for the future.

Finding structures that work can lead to designs that work better at lower cost with more abundant materials. Research and development takes those steps, a break through is not always ready for production right away.

Selenium Sulfide is selling at $400/tonne to $600/tonne in China with minimun order of 5 to 20 tonnes.

At that low price it is probably not that rare or difficult to make?

They've tried sulfur, now its selenium, perhaps tellurium will be next. You never know.

Incidentally, selenium is a by product of copper refining. Most produced in the West is consumed by China. Maybe they can trade the rest of us some of their rare earths for magnetic materials.

Like lithium, there's a lot of selenium in ocean water.

If this works and creates demand then we'll probably see people working on ways to economically extract it.

What would really be great would be to extract it from the southern Central Valley of California where selenium concentrations have ruined farmland.

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