Girishkumar

Four different architectures of Li-air batteries, which all assume the use of lithium metal as the anode. The three liquid electrolyte architectures are aprotic, aqueous, and a mixed aprotic-aqueous system. In addition, a fully solid state architecture is also given. Credit, ACS, Girishkumar et al. Click to enlarge.

While the practical energy density of Li-air batteries could approach that of gasoline—after factoring in tank-to-wheel efficiencies—and thereby enable a transition to an electrified road transportation system, there are challenges facing the development of commercial Li-air batteries and the current understanding of their electrochemistry, according to a Perspective by a team of researchers from IBM Research-Almaden published in ACS’ Journal of Physical Chemistry Letters.

IBM and its partners have launched a multi-year research initiative exploring rechargeable Li-air systems: The Battery 500 Project. (Earlier post.) The “500” stands for a target range of 500 miles/800 km per charge, which translates into a battery capacity of about 125 kWh at an average use of

250 Wh/mile for a standard family car.

…the requirements for large capacity automotive

propulsion batteries are extensive, but quite well defined. They will serve as guidelines for the research to be carried out on Li-air systems. At present, automotive propulsion batteries are just beginning the transition from nickel

metal hydride to Li-ion batteries, after nearly 35 years of research and development on the latter. The transition to Li-air batteries (if successful) should be viewed in terms of a similar development cycle.

—Girishkumar et al.

Basics. The energy density of gasoline is approximately 13,000 Wh/kg. With a current average tank-to-wheel efficiency of 12.6%, the usable energy density of gasoline in an automotive application is about 1,700 Wh/kg.

Since the efficiency of electric propulsion systems (battery-to-wheels) are about 90%, a 10-fold improvement of the current energy densities of Li-ion batteries, which are typically between 100 and 200 Wh/kg (cell level), would bring electric propulsion systems on-par with

gasoline, at least as measured by gravimetric energy density. However, there is no expectation that current batteries such as Li-ion will ever come close to the target of 1700 Wh/kg. New

chemistries are required to achieve this goal.

The oxidation of 1 kg of lithium metal releases 11,680 Wh/kg,

not much lower than that of gasoline…However,

practical energy densities for Li-air batteries will be far less.

Existing metal-air batteries, such as Zn/air, typically have a practical

energy density of about 40-50% of their theoretical density.

However, one can safely assume that even fully developed Li-air

cells will never achieve such an excellent ratio, because lithium is

very light, and therefore the overhead of the battery structure,

electrolytes, and so forth will have a much larger impact.

Fortunately, an energy density of 1700 Wh/kg for the fully

charged battery corresponds only to 14.5% of the theoretical

energy content of lithium metal. It is not inconceivable that

such an energy density, at the cell level, may be achievable,

given intensive and long-term development work. The energy

density of the complete battery system may be only half of the

density realized at the cell level.

—Girishkumar et al.

Considerations for Li-air systems include:

  • Power density and cost. While Li-air systems offer the promise of very high energy densities, their power density is currently very low.

    Prototype aprotic Li-air cells

    deliver current densities in the order of 1 mA/cm2. It will be

    critical to increase this current density by at least 1 order of

    magnitude. Even then, the macroscopic surface area to supply

    the total power for a propulsion battery is very large. For

    example, a battery with 100 kW power output at a cell voltage

    of 2.5 V and a current density of 25mA/cm2 will require a total

    internal surface area of 160 m2, equal to the internal surface of

    the human lung.

    —Girishkumar et al.

    One way around the power issue would be to utilize a hybrid system where a small capacity but high power battery, for example, provides power for short periods of high demand, such as during acceleration, the authors suggest.

  • Electrical energy efficiency. Current Li-air cells have a charging voltage that is considerably higher than the discharge voltage (overvoltage). This corresponds to a low cycle electrical energy efficiency, currently on the order of 60-70%, the authors note. Practical propulsion batteries should exhibit “round-trip” energy efficiencies of 90%. The detailed mechanisms underlying these high over voltages are currently

    not understood.

  • Lifetime and Cyclability. Current Li-air cells have been demonstrated with up to about 50 cycles with only moderate

    loss in capacity. Therefore, the authors suggest, future research efforts need to focus on improving the capacity retention during cycling.

  • Safety. Typical thermal runaway of a Li-ion battery due to overcharging or internal shorts is not a possibility in Li-air batteries

    because of the rate-limited surface nature of the reaction, i.e.,

    the reactant O2 is not stored in the battery.

    However, there are two other safety concerns to be considered. First, the desired, though not mandatory, use of lithium metal anodes is a

    well-known safety problem, since lithium metal tends to form

    dendrites, which can short-circuit the battery and react aggressively with many contaminants. Second, the presumed

    dominant reaction product of aprotic cells is Li2O2, which

    is a strong oxidizer. Combined with an organic electrolyte,

    this could lead to safety issues in an accident. However,

    preliminary experiments at IBM indicate that no thermal

    exothermic reactions between Li2O2 and common electrolytes

    occur at temperatures below the melting point of lithium

    metal (180 °C). This safety concern does not exist in aqueous

    cells.

    —Girishkumar et al.

Architectures. There are currently four chemical

architectures for Li-air batteries under investigation globally, including three versions with liquid electrolytes—a fully aprotic liquid electrolyte; an aqueous electrolyte; and a mixed system with an aqueous electrolyte immersing the cathode and an aprotic electrolyte immersing the anode—and an all-solid-state battery with a solid electrolyte. Only the aprotic configuration of a Li-air battery has shown any promise of electrical rechargeability; hence, this configuration is attracting the most effort to date, according to the authors.

The fundamental electrochemistry—which is not fully understood in detail—depends upon the electrolyte around the cathode, the authors note.

Aprotic

Schematic operation proposed for the rechargeable

aprotic Li-air battery. During discharge, the spontaneous electrochemical

reaction 2Li+O2→Li2O2 generates a voltage of 2.96 V at equilibrium (but practically somewhat less due to overpotentials).

During charge, an applied voltage larger than 2.96 V (~4 V is

required due to overpotentials) drives the reverse electrochemical

reaction Li2O2→2Li + O2. Credit: ACS, Girishkumar et al. Click to enlarge.

Aprotic Li-air battery. A “typical” aprotic design would consist of a metallic lithium anode, an electrolyte comprising a dissolved lithium salt in an aprotic solvent and a porous O2-breathing cathode composed of large surface area carbon particles and catalyst particles, bound to a mesh using a binder.

In addition to a detailed discussion of the possible dynamics of the electrochemistry of the cell, the authors note that there are other issues that need to be addressed, including the lithium anode, as well as the question of Li-air or Li-O2 batteries—e.g., whether or not to deploy a membrane that selectively permeates O2 to avoid unwanted parasitic reactions with components such as water, carbon dioxide, carbon monoxide and nitrogen in ambient air.

Recommended key research. To develop and commercialize a practical, rechargeable Li-air battery, the authors recommend research in the following key areas:

  1. Quantitative understanding of the electrochemical reactions

    and their relationship to the discharge/charge

    currents. This is the key to quantitatively demonstrating

    chemical reversibility and understanding Coulombic

    efficiency of the battery in cycling.

  2. Development of oxidation-resistant electrolytes and

    cathodes that can withstand high oxidation potentials

    in the presence of O2. This is also essential for chemical

    reversibility and Coulombic efficiency in the battery

    cycling.

  3. Understanding the nature of electrocatalysis for Li-air

    batteries where insoluble products are formed and

    the development of cost-effective catalysts to reduce

    overpotentials for the discharge and charge reactions.

    This is key to enhancing power density in discharge,

    electrical efficiency in a discharge-charge cycle, and

    ultimately in cycle life (due to possible electrolyte

    oxidation).

  4. Development of new nanostructured air cathodes

    that optimize transport of all reactants (O2, Li+, and electrons) to the active catalyst surfaces and provide appropriate space for solid lithium oxide products. This is required to maintain capacity at

    higher power densities. A new realization is that minimizing

    difficulties due to electron transport through

    the lithium oxide solid products in the cathode is

    important.

  5. Development of a robust lithium metal or lithium

    composite electrode capable of repeated cycling at

    higher current densities. This will most likely require

    development of a protective layer that limits the deleterious

    effects of environmental contamination on the

    lithium and inhibits dendrite growth.

  6. Development of high throughput air-breathing membranes

    (or other mechanisms) that separate O2 from

    ambient air in order to avoid H2O, CO2, and other

    environmental contaminants from limiting the lifetime

    of Li-air batteries.

  7. Understanding the origin of the temperature dependencies

    in Li-air batteries and minimizing their adverse

    effects.

Resources

  • G. Girishkumar, B. McCloskey, A. C. Luntz, S. Swanson and W. Wilcke (2010) Lithium-Air Battery: Promise and Challenges. J. Phys. Chem. Lett., doi: 10.1021/jz1005384