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Antimony nanocrystals as high-capacity anode materials for both Li-ion and Na-ion batteries

19 March 2014

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TEM image (false colored) of monodisperse antimony nanocrystals. (Photo: Maksym Kovalenko Group / ETH Zürich) Click to enlarge.

Researchers from ETH Zürich and Empa have succeeded for the first time in producing uniform (monodisperse) antimony (Sb) nanocrystals (NCs). The nanocrystals possess high and similar Li-ion and Na-ion charge storage capacities of 580−640 mAh g−1 at moderate charging/discharging current densities of 0.5−1C (1C-rate is 660 mA g−1).

At all C-rates (0.5−20C), capacities of 20 nm Sb particles are systematically better than for both 10 nm and bulk Sb. At 20C-rates, retention of charge storage capacities by 10 and 20 nm Sb nanocrystals can reach 78−85% of the low-rate value, indicating that rate capability of Sb nanostructures can be comparable to the best Li-ion intercalation anodes and is so far unprecedented for Na-ion storage. A paper on their work appears in the ACS journal Nano Letters.

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Rate-capability tests of (A) Li-ion and (B) Na-ion half-cells employing Sb (antimony) anodes made from monodisperse colloidal Sb nanocrystals (NCs) and from microcrystalline powders. The data for 10 nm Sn (tin) NCs are shown for comparison. All anodes had the same composition of Sb(64%)/CB(21%)/ CMC(15%) and were cycled at room temperature under variable current rate of 0.5−20C (1C = 0.66 Ah g−1, 9 cycles at each C-rate, first cycle at 0.1C).

One molar LiPF6 in ethylene carbonate/dimethyl carbonate mixture containing 3 wt % of FEC was used as electrolyte for Li-ion cells, whereas 1 M NaClO4 in propylene carbonate containing 10 wt % of FEC was used for Na-ion batteries.

All batteries were cycled in the 20 mV to 1.5 V potential range. The obtained capacities were normalized by the mass of Sb. Credit: ACS, He et al. Click to enlarge.

Antimony has long been regarded as a promising anode material for high-performance lithium-ion batteries as this metalloid exhibits a high charging capacity—a factor of two higher than that of commonly used graphite. Initial studies revealed that antimony could be suitable for both rechargeable lithium- and sodium-ion batteries because it is able to store both kinds of ions. Sodium is regarded as a possible low-cost alternative to lithium as it is much more naturally abundant and its reserves are more evenly distributed on Earth.

For antimony to achieve its high storage capability, however, it needs to be produced in a special form. The researchers managed to chemically synthesize monodisperse antimony nanocrystals that were between ten and twenty nanometers in size.

The full lithiation or sodiation of antimony leads to large volumetric changes. By using nanocrystals, these modulations of the volume can be reversible and fast, and do not lead to the immediate fracture of the material. An additional important advantage of nanocrystals (or nanoparticles) is that they can be intermixed with a conductive carbon filler in order to prevent the aggregation of the nanoparticles.

Electrochemical tests showed Maksym Kovalenko and his team that electrodes made of these antimony nanocrystals perform equally well in sodium and in lithium ion batteries. This makes antimony particularly promising for sodium-ion batteries because the best lithium-storing anode materials (Graphite and Silicon) do not operate with sodium.

Highly monodisperse nanocrystals, with the size deviation of ten percent or less, allow identifying the optimal size-performance relationship. Nanocrystals of ten nanometers or smaller suffer from oxidation because of the excessive surface area. On the other hand, antimony crystals with a diameter of more than 100 nanometers aren’t sufficiently stable due to the massive volume expansion and contraction during the operation of a battery. The researchers achieved the best results with 20 nanometer large particles.

The researchers also identified a size-range of around 20 to 100 nanometers within which this material shows excellent, size-independent performance, both in terms of energy density and rate-capability.

These features even allow using polydisperse antimony particles to obtain the same performance as with very monodisperse particles, as long as their sizes remain within this size-range of 20 to 100 nanometers.

This greatly simplifies the task of finding an economically viable synthesis method. Development of such cost-effective synthesis is the next step for us, together with our industrial partner.

—Maksym Kovalenko

Experiments of his group on monodisperse nanoparticles of other materials show much steeper size-performance relationships such as quick performance decay with increasing the particle size, placing antimony into a unique position among the materials which alloy with lithium and sodium.

However, production of a sufficient number of high-quality uniform antimony nanocrystals is still too expensive to make short-term commercialization possible. Kovalenko estimates that tt will be another decade or so before a sodium-ion battery with antimony electrodes could hit the market.

All in all, batteries with sodium-ions and antimony nanocrystals as anodes will only constitute a highly promising alternative to today’s lithium-ion batteries if the costs of producing the batteries will be comparable.

—Maksym V. Kovalenko

Resources

  • He M, K Kravchyk, Walter M, Kovalenko MV (2014) “Monodisperse Antimony Nanocrystals for High-Rate Li-ion and Na-ion Battery Anodes: Nano versus Bulk,” Nano Lett. doi: 10.1021/nl404165c

March 19, 2014 in Batteries | Permalink | Comments (3) | TrackBack (0)

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Comments

This is really old news, like decades old. Antimony (Sb) is relatively poisonous. It is not as bad, but similar to arsenic (AS). In fact they are in the same family of elements. They are right next to ech other right along the metalloid line and in the nitrogen family. Of course, they could be handled safely for sure. However, I know they won't be because technical people are discounted in this world of fake talking heads.

"Kovalenko estimates that tt will be another decade or so before a sodium-ion battery with antimony electrodes could hit the market."

Its just an anode, yet computing power and general knowledge increase by over 30 fold in that much time.

Antimony is a rare element (0.2 ppm), in its abundance comparable for instance to indium. There is 50x more Li in the lithosphere than Sb, so all this hype about replacing it by more abundant Na, thanks to Sb, is just nonsense.

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