Sodium-ion Batteries

a low-cost alternative to Li-ion batteries

Hallie Sala Cluster 8: Chemistry of Life COSMOS 2013

Abstract In recent years, we have become increasingly dependent on lithium-ion batteries to power our laptops, phones, other portable electronics, andmost recentlyelectric vehicles (EV's). However, much of the world's lithium is tied up in undeveloped or unstable regions of the world, making extraction difficult and costly. Consequently, the economics of the situation favor a shift towards the employment of sodium-ion batteries. In contrast to lithium, sodium is incredibly cheap and is found nearly everywhere on the planet. Because of the low cost of the batteries, a shift towards usage of the devices in everyday life would likely promote increased access to various technologies, especially EV's. Additionally, with some modifications, sodium-ion batteries could easily become a vital component in the storage of renewable-source energy in smart electric grids which integrate discontinuous energy flow. However, current sodium-ion batteries are simply not as advanced as lithium-ion batteries; much work is needed in the field before sodium-ion batteries can replace lithiumion batteries on a large scale. In particular, new electrode materials better suited to sodium intercalation must be developed.

1. Background Lithium-ion batteries, first proposed by M. S. Whittingham in the early 1970s, are, as things go, excellent batteries. They have a very high energy density, hold their charge, can handle hundreds of cycles, and have no memory effect. These features have found Li-ion batteries a home inside many portable electronics, including most laptops and mobile phones (Vinokudmar). Inside a Li-ion battery, most of the chemistry happens in three thin sheets composed of variable materials: the positive electrode, negative electrode, and between them, a separator often made of microperforated plastic. The sheets are submerged in a solvent which acts as an electrolyte. Common solvents include organic carbonates and esters. Because of safety issues (spontaneous combustion

being one) with the use of lithium-metal electrodes, other materials are used in both anode and cathode to essentially hold the Li ions when they are not in use. Although a wide variety of electrode materials have been employed in Li-ion batteries, to varying effects, one of the most common in graphite. The lithiation of graphite is reversible, allowing the battery to be rechargeable, and thermodynamically favorable. Other materials used have often been lithium compounds, such as LiCoO2 in the positive electrode and lithium transition metal nitrides in the negative (Vinokudmar 2). The basic mechanism by which a Li-ion battery works is fairly simple. During discharge, a current is run through the lithiated anode material, causing electrons to flow from the anode to cathode. To compensate for the difference in charge, Li-ions 'follow' the electrons, crossing the separator into the cathode (fig. 1). When the battery charges, this process is reversed. Fig. 1 Despite occasionally

bursting into flame, Li-ion batteries remain an excellent source of energy. Per kilogram of material, Liion batteries store more than half-again as much energy as a NiMH battery pack, and six times as much energy as a lead-acid battery (Brain 1). This is not to say Li-ion batteries are perfect. Limited battery life, temperature sensitivity, and the much-mentioned spontaneous combustion problem are a few of their more negative characteristics. However, the most pressing problem as regards most applications relates not to their chemical properties but rather the economic realities of the lithium supply. Most of the world's lithium is located in undeveloped or unstable regions; extracting it has proved difficult. Although as much as half the

world's lithium lies under the Bolivian Salar de Uyuni salt flats, the resource is almost entirely untapped. In his article In Bolivia, Untapped Bounty Meets Nationalism, Simon Romero of the New York Times cites a growing nationalist sentiment about the lithium as a factor which has led the Bolivian government, led by President Evo Morales, to deny foreign companies permission to extract the metal. Because of the unstable state of the lithium supply, alternative technologies promising similar characteristics are looking increasingly attractive. Enter the Na-ion battery. On first glance, it appears to meet all requirements. Sodium is cheap and abundant in the form of NaCl; no single country or region holds a monopoly on production. Also helpful is that the insertion chemistry of sodium is similar enough to that of lithium that Na-ion battery technology is already somewhat developed. However, these positive traits are not enough to mask the fact that current Na-ion batteries are simply not powerful enough to replace Li-ion batteries. Much work must be done in determining possible new electrode materials and electrolytes better suited to sodium before these batteries can be considered commercially viable.

2. Sodium-Ion Batteries Na-ion batteries are very similar in design to Li-ion. Consequently, many of the most studied electrode materials in Na-ion batteries were first utilized in their lithium counterparts. However, research has shown that what works for lithium doesn't necessarily work for sodium; many of the best electrode materials as paired with lithium, such as graphite, have proved disappointing in combination with sodium. Thus, the search for commercially viable Na-ion batteries demands finding and optimizing new electrode materials and electrolytes (Palomares et al. 2). Additionally, it must be recognized that Na-ion batteries, which differ in significant ways from Li-ion batteries in possessing lower energy density, voltage, and cost, cannot be employed as a simple

substitution for their Li-ion predecessors. Different characteristics demand different treatment; Na-ion batteries may be best used in places where Li-ion batteries have not been employed to great success. One potential application of Na-ion batteries is in storing renewable source energy in smart electric grids that integrate discontinuous energy flow optimizing the performance of clean energy sources (Palomares et al. 1) Because household and commercial energy usage is inconsistent throughout the day, typically peaking in late afternoon and falling during the night, storage systems are needed to hold excess energy produced in off-peak hours to be used later. Sodium's low cost and enormous availability make Na-ion batteries ideal for this purpose. However, further development is needed before Na-ion batteries are sufficiently advanced to be employed in this way.

3. New Materials The most pressing concern in improving Na-ion batteries to a point where they can be utilized in commercial applications is the development of suitable electrode materials. While Li-ion electrode materials have served as a starting place for research into Na-ion materials, it is clear that Na-ion batteries will require new materials optimized for Na charge carrier ions. According to Hong et al., the larger size and different bonding characteristics of sodium ions influence the thermodynamic and/or kinetic properties of sodium-ion batteries, which leads to unexpected behavior in electrochemical performance and reaction mechanism, compared to lithium-ion batteries (1). For instance, graphite, commonly used in the anode of Li-ion batteries, performs unfavorably in Na-ion cells. In the research described in Charge carriers in rechargeable batteries: Na ions vs. Li ions, Hong et al. demonstrated that while reversible de/insertion of Li ions into graphite is observed for the lithiumgraphite cell, the sodiumgraphite cell showed irreversible sodiation with a negligible amount of de/sodiation. Because of the chemical softness of the Na-C bond, the

interaction between the guest sodium and the graphene layer becomes very weak, explaining the discrepancy (6). Disordered carbon, hard carbon, and hollow carbon nanowires interacted better with Na ions than did graphite, but still fell short of the Li-ion standard.

Some of the most promising electrode materials so far are phosphorous-based materials. Originally introduced as electrode materials for Li-ion batteries, phosphorous-based materials demonstrate high specific capacity, which is an extremely favorable characteristic due to the low energy density of Na-ion cells. Crystalline black, amorphous black, crystalline red, and amorphous red phosphorous have all shown reversible lithiation in Li-ion batteries and may respond similarly to

sodium. A phosphor ouscontainin g compoun d of particular interest is Olivine NaFePO4 , due to its high theoretica l specific capacity. However, very little Fig. 2 Voltagecapacity plots of (A) negative and (B) positive electrode materials for research NIBs. Reproduced from "Charge carriers in rechargeable batteries: Na ions vs. Li ions" by Hong et al. has been done involving Na-ion batteries and phosphorous-based electrodes so far (Hong et al.). Other possible electrode materials include LiNiN (Cabana 1), transition metal fluorides, and alluadite framework compounds (Palomares 12)

4. Conclusions Although current technology remains inadequate to support widespread implementation, Na-ion batteries remain a promising source of energy for the future. Because of the low cost and high availability of elemental sodium compared to lithium, Na-ion batteries are an increasingly attractive option for use in portable electronics, EV's, and smart grids for renewable-source energy storage. With the adoption of new electrode materials (possibly including phosphorous-based materials), it is conceivable that Na-ion cells may soon be improved to such a level as surpasses Li-ion cells in usefulness for many applications. The benefits of commercially viable Na-ion batteries are immediate and obvious: lowered costs for portable electronics, EV's, renewable-source energyeverything employing a metal-ion battery.

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