New Chemistry Could Overcome Key Drawbacks of Lithium-air Batteries

Lithium-air batteries are considered highly promising technologies for electric cars and portable electronic devices because of their potential for delivering a high energy output in proportion to their weight. But such batteries have some pretty serious drawbacks: They waste much of the injected energy as heat and degrade relatively quickly. They also require expensive extra components to pump oxygen gas in and out, in an open-cell configuration that is very different from conventional sealed batteries. 

But a new variation of the battery chemistry, which could be used in a conventional, fully sealed battery, promises similar theoretical performance as lithium-air batteries, while overcoming all of these drawbacks.

The new battery concept, called a nanolithia cathode battery, is described in the journal Nature Energy in a paper by Ju Li, the Battelle Energy Alliance Professor of Nuclear Science and Engineering at MIT; postdoc Zhi Zhu; and five others at MIT, Argonne National Laboratory, and Peking University in China.

One of the shortcomings of lithium-air batteries, Li explains, is the mismatch between the voltages involved in charging and discharging the batteries. The batteries’ output voltage is more than 1.2 volts lower than the voltage used to charge them, which represents a significant power loss incurred in each charging cycle. “You waste 30 percent of the electrical energy as heat in charging. … It can actually burn if you charge it too fast,” he says.

Staying solid

Conventional lithium-air batteries draw in oxygen from the outside air to drive a chemical reaction with the battery’s lithium during the discharging cycle, and this oxygen is then released again to the atmosphere during the reverse reaction in the charging cycle.

In the new variant, the same kind of electrochemical reactions take place between lithium and oxygen during charging and discharging, but they take place without ever letting the oxygen revert to a gaseous form. Instead, the oxygen stays inside the solid and transforms directly between its three redox states, while bound in the form of three different solid chemical compounds, Li₂O, Li₂O_2, and LiO₂, which are mixed together in the form of a glass. This reduces the voltage loss by a factor of five, from 1.2 volts to 0.24 volts, so only 8 percent of the electrical energy is turned to heat. “This means faster charging for cars, as heat removal from the battery pack is less of a safety concern, as well as energy efficiency benefits,” Li says.

This approach helps overcome another issue with lithium-air batteries: As the chemical reaction involved in charging and discharging converts oxygen between gaseous and solid forms, the material goes through huge volume changes that can disrupt electrical conduction paths in the structure, severely limiting its lifetime.

The secret to the new formulation is creating minuscule particles, at the nanometer scale (billionths of a meter), which contain both the lithium and the oxygen in the form of a glass, confined tightly within a matrix of cobalt oxide. The researchers refer to these particles as nanolithia. In this form, the transitions between LiO₂, Li₂O_2, and Li₂O can take place entirely inside the solid material, he says.

The nanolithia particles would normally be very unstable, so the researchers embedded them within the cobalt oxide matrix, a sponge-like material with pores just a few nanometers across. The matrix stabilizes the particles and also acts as a catalyst for their transformations.

Conventional lithium-air batteries, Li explains, are “really lithium-dry oxygen batteries, because they really can’t handle moisture or carbon dioxide,” so these have to be carefully scrubbed from the incoming air that feeds the batteries. “You need large auxiliary systems to remove the carbon dioxide and water, and it’s very hard to do this.” But the new battery, which never needs to draw in any outside air, circumvents this issue.

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