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The lithium-air battery [Li-air] is a battery chemistry that uses the oxidation of lithium at the anode and reduction of oxygen at the cathode to induce a current flow. Originally proposed in the 1970’s as a possible power source for electric vehicles, Li-air batteries recaptured scientific interest in the late 2000’s due to advances in materials technology and an increasing demand for environmentally-safe and oil-independent energy sources. Currently, four types of Li-air batteries are being pursued: aprotic[1][2], aqueous[3], solid state[4], and mixed aqueous/aprotic[5].

The major appeal of the Li-air battery is the extremely high energy density, a measure of the amount of energy a battery can store for a given volume, which rivals that of traditional gasoline powered engines. Li-air batteries gain this advantage in energy density by utilizing the oxygen in air, eliminating the need for a Li-air battery to store fuel (oxygen) at the cathode.

The technology is still in its infancy and will require significant funding and research efforts in a variety of fields, however, scientists and industry alike see potential in its development with IBM leading a research effort to develop a Li-air battery capable of driving a commercial vehicle 500 miles on a single charge [6].

Background and Significance

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Lithium based batteries have received considerable attention over the past 40 years, especially since the introduction of the first commercial cells 20 years ago. Lithium based batteries have shown high performance mostly in part to the high specific energy densities intrinsic to lithium based materials [7]. Coincident with investigation of lithium battery technologies, metal-air batteries, specifically zinc, have received attention due to the very high energy densities associated with their design. Specifically, the high theoretical specific energy densities for metal-air batteries are possible due to the use of atmospheric oxygen as the cathode, eliminating a traditional cathode structure. The first true rechargable lithium-air battery was proposed by Abraham and Jiang. in 1996. [8] Recently, lithium-air batteries have been proposed as the next step in lithium battery architecture, due to the high specific energy density of lithium with respect to air (3840 mAh/g). [9]

Currently, many challenges prevent the realization of high-performance lithium-air batteries. Substantial difficulties are faced in preparing structures for the precipitation of lithium oxide or lithium peroxide at the cathode. In addition, the cathode must be made electrically conductive. Currently, porous carbon electrodes are the material of choice, but pore clogging by lithium oxide or lithium peroxide in aprotic systems must be balanced with the need for oxygen permeation. Several catalysts have been used to improve cathode performance, with MnO2 being the material of choice. The actual mechanism of improvement due to catalyst activity is not yet clear, but it is theorized it may alter the structure of the oxide deposits [10] [11]. Significant challenges have also been faced at the pure lithium anode. Dendritic lithium deposits, long a problem in lithium-ion batteries, can eventually lead to shorting of the battery. In addition, current electrolytes are often unstable with respect to the lithium anode, necessitating a need for new electrolytes or a redesigned electrolyte/anode interface. Further complicating the design of lithium-air batteries is degradation of battery materials by atmospheric contaminants, such as water vapor [1].

Despite the need for innovation in key areas of research and design related to creating a fully-functional, high-efficiency lithium-air battery, the applications of such a battery are far reaching. The significant increase in energy density afforded by a lithium-air battery opens opportunities for lithium based power storage that current lithium based batteries could not hope to fulfill. A major driving forces in lithium-air battery development is the demand for advanced battery technology for the automotive sector. The energy density of gasoline is approximately 13 kWh/g, which corresponds to 1.7 kWh/kg of energy provided to the wheels when accounting for losses. The theoretical energy density of the lithium-air battery is 12 kWh/kg, and it has been theorized that a practical energy density of 1.7 kWh/kg at the wheels of an automobile could be realized when accounting for the much higher efficiency of electric motors [6]. In a nearer future, proponents of the technology expect lithium-air batteries to replace the lithium-ion batteries currently powering portable electronic devices. Lithium-air batteries have the potential to have 5-15 times the energy density of current lithium-ion batteries. Thus even the most conservative estimates indicate that a modern-day lithium-ion battery may someday be replaced by a lithium-air battery 1/5 the size or a lithium-air battery with a lifespan 5 times as long. Whether lithium-air batteries lead to reduced battery sizes or longer lasting batteries, the potential for a vast reduction in electronic waste is an attractive consequence of developing such battery technology [12].

Principles of Operation

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Schematic of lithium-air battery charge and discharge cycles

Although the electrochemical details vary by battery design (and consequently electrolyte type), in general, lithium is oxidized at the anode forming lithium ions and an electrons. The electrons follow the external circuit to do electric work and the lithium ions migrate across the electrolyte to reduce oxygen at the cathode. When an externally applied potentials is greater than the standard potential for the discharge reaction, lithium metal is plated out on the anode, and O2 is generated at the cathode. [13]

Schematic of artificial vs. spontaneous electrolyte interface

Anode

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Lithium metal is the current choice of anode material for Li-air batteries. At the anode, electrochemical potential forces the lithium metal to give off electrons as per the oxidation. The half reaction is given below: [14]

Li ↔ Li + e-

Lithium has high specific capacity (3842 mAh/g) compared with other metal-air battery materials (2965 mAh/g for Zinc, 2965 mAh/g for aluminum) making it an excellent choice for an anode material.[7] However, there are some issues associated with metallic lithium as the anode. Upon charging/discharging in aprotic cells, a multilayer deposition of lithium salts creates a mass diffusion barrier between the lithium and electrolyte which initially prevents further corrosion of the lithium metal but eventually inhibits the reaction kinetics between the anode and the electrolyte.[15] This chemical heterogeneity of the solid-electrolyte interface (SEI) results in morphologically heterogeneous structure prone to non-uniform current distributions. Uneven current distributions further the dendrite growth and typically leads to a short between the anode and cathode.[16] Also, In aqueous cells problems at the SEI stem from the high reactivity of lithium metal with water.[17]

Several approaches have been taken to overcome problems at the SEI associated with lithium metal anodes.

1. Formation of a Li-ion conductive artificial protective layer using novel di- and triblock copolymer electrolytes. [18]
According to Seeo, Inc.[18] The electrolytes made from di- and triblock copolymer (e.g. polystyrene with the high Li-ion conductivity of a soft polymer segment, such as a poly(ethylene oxide PEO/ Li-salt mixture) ) combine the mechanical stability of a hard polymer segment, which will inhibit dendrite shorts via mechanical blocking, with the high ionic conductivity of the soft polymer/lithium salt mixture.
2. Use of a Li-ion conducting glass or glass-ceramic material. [19][20][4]
Li-ion conducting ceramic materials are (generally) readily reduced by lithium metal, and therefore a thin film of a lithium stable conducting material, such as Li3P or Li3N, could be inserted between the ceramic and metal. This ceramic based artificial SEI would not only inhibit the formation of dendrites, but would also protect the lithium metal from atmospheric contamination.

Cathode/Electrolyte

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At the cathode, reduction occurs by the recombination of lithium ions with oxygen. Currently, mesoporous carbon has been used as a cathode material with metal catalysts.[21] Metal catalysts incorporated into the carbon electrode enhance the oxygen reduction kinetics and increase the specific capacity of the cathode.[12] Manganese, cobalt, ruthenium, platinum, silver, or a mixture of cobalt and manganese are currently used as metal catalysts. A study by Abraham et al found that manganese catalyzed cathodes performed best, with a specific capacity of 3137 mAh per gram carbon, and cobalt catalyzed cathodes performed second best, with a specific capacity of 2414 mAh per gram carbon.[8]

The Li-air cell performance is limited by the efficiency of reaction at the cathode because most of the cell voltage drop occurs at the cathode.[7] Thus, improvement of cathode in a Li-air battery is essential for overall Li-air cell performance enhancement. Currently, there exist multiple battery chemistry (for more see battery designs) delineated by electrolyte choice, so the exact electrochemical reaction at the cathode varies between Li-air batteries. The discussion below is focused on aprotic and aqueous electrolytes as the exact electrochemistry taking place in solid-state electrolytes is not well understood.

In a cell with an aprotic electrolyte lithium oxides are produced through reduction at the cathode:

Li+ + e- + O2 + * → LiO2*
Li+ + e- +LiO2* → Li2O2*
Where a "*" denotes a surface site on Li2O2 where the growth proceeds which is essentially a neutral Li vacancy in the Li2O2 surface.

It should be noted that lithium oxides are insoluble in aprotic electrolytes which leads to the cathode clogging. [22]

In a cell with an aqueous electrolyte the reduction at the cathode can also produce lithium hydroxide:

  • Acidic electrolyte
2Li + ½ O2 + 2H+ → 2Li++ H2O
A conjugate base is involved in the reaction. The theoretical maximal Li-air cell specific energy and Li-air cell energy density is 1400 Wh/Kg and 1680 Wh/L respectively. [6]
  • Alkaline aqueous electrolyte
2Li + ½ O2 + H2O → 2LiOH
Water molecules are involved in the redox reactions at the air cathode. The theoretical maximal Li-air cell specific energy and Li-air cell energy density is 1300 Wh/Kg and 1520 Wh/L respectively [6]


The development of new cathode materials must account for the accommodation of substantial amounts of LiO2, Li2O2, and/or LiOH without causing a blockage of the cathode pores and find suitable catalysts to make the electrochemical reactions energetically practical.

  • As an example, dual pore system materials are the most promising in terms of energy capacity. [23]
  • The first pore system of the material serves as an oxidation product storage
  • The second pore system of the material serves as transports oxygen.

Li-Air Battery Designs

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Efforts in Li-air batteries have focused on four different chemical designs. All the designs have distinct advantages and significant associated technological challenges. It remains to be seen which design will become the standard for Li-air batteries of tomorrow.

Schematic of aprotic type Li-Air battery design

Aprotic

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Most worldwide effort on Li-air batteries has focused on the aprotic battery design. The aprotic design consists of a lithium metal anode, a liquid organic electrolyte, and a porous carbon cathode. Electrolytes can be made of any organic capable of solvating lithium salts (LiPF6, LiAsF6, LiN(SO2CF3)2, and LiSO3CF3), but have typically consisted of carbonates, ethers, and esters[13]. The carbon cathode is usually made of a high surface area carbon material with a nanosized metal oxide catalyst (commonly MnO2 or Mn3O4). A major design advantage of the aprotic battery is the spontaneous formation of a barrier between the anode and electrolyte (much like the barrier formed between electrolyte and carbon-lithium anodes in conventional Li-ion batteries) which protects the lithium metal from further reaction with the electrolyte. Practically, the aprotic battery design draws interest as it has been shown to be rechargeable[6]. However, it has major drawbacks in that Li2O2 produced at the cathode is generally insoluble in the organic electrolyte leading to build up along the cathode/electrolyte interface. This makes cathodes in aprotic batteries prone to clogging and volume expansion which reduces conductivity and degrades battery performance over time.[3][17]

Schematic of aqueous type Li-Air battery design

Aqueous

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The aqueous Li-air battery consists of a lithium metal anode, an aqueous electrolyte, and a porous carbon cathode. The aqueous electrolyte is simply a combination of lithium salts dissolved in water. The aqueous Li-air battery avoids the issue of cathode clogging experienced in aprotic batteries because the reaction products are water soluble, which allows aqueous Li-air batteries to maintain performance over time[3]. The aqueous design also has a higher practical discharge potential than its aprotic counterpart. However, lithium metal reacts violently with water and thus the aqueous design requires a solid electrolyte interface between the lithium metal and aqueous electrolyte. Commonly, a lithium conducting ceramic or glass is used, but conductivities are generally low (on the order of 10-3 S/cm at ambient temperatures).[17]

Schematic of a mixed aqueous-aprotic type Li-Air battery design

Mixed Aqueous/Aprotic

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The aqueous/aprotic or mixed Li-air battery design is an attempt to unite advantages of both the aprotic and aqueous battery designs. Although there exist multiple hybrid designs, the common feature of these designs is a separated two-part (one part aqueous and one part aprotic) electrolyte connected by a lithium conducting membrane. A lithium metal anode is in contact with the aprotic side of the electrolyte while the porous cathode is in contact with the aqueous side. A lithium conducting ceramic is typically employed as the membrane joining the two electrolytes.[3][6]

Schematic of solid-state type Li-Air battery design

Solid State

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The solid-state battery design eliminates problems at the anode/cathode interfaces associated with using a liquid electrolyte. It is also attractive from a safety standpoint as organic solvents, currently used in lithium-ion batteries (and employed in the aprotic Li-air battery design), are flammable and at high temperatures the use of an organic electrolyte can lead to rupture and ignition of the battery.[4] Current solid-state Li-air batteries use a lithium anode, a ceramic, glass, or glass-ceramic electrolyte, and a porous carbon cathode. The anode and cathode are typically separated from the electrolyte by polymer-ceramic composites which enhance charge transfer at the anode and electrochemically couple the cathode to the electrolyte. The polymer-ceramic composites serve to reduce the overall impedance of the solid-state Li-air battery. The main drawback of the solid-state battery design is the low conductivity of most glass-ceramic electrolytes. Lithium aluminum germanium phosphate has been found to be an effective electrolyte, but the ionic conductivity of current lithium fast ion conductors are still lower than liquid electrolyte alternatives. [9]

Challenges

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There are many challenges facing the design of Li-air batteries, which currently limits their use to the laboratory. One of the largest challenges lies in keeping the battery protected from the environment. Atmospheric oxygen must be present at the cathode, but the cathode can be degraded by humidity.

Cathode

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Most of the current limitations in Li-air battery development are seen at the cathode. One of the problems seen is incomplete discharge due to blockage of the porous carbon cathode with discharge product. The effect of pore size and pore size distribution is still poorly understood.[7] Production of a cathode with high a pore size and ability to hold a large amount of Li2O2 (lithium peroxide) is essential to Li-air battery development. Catalysts have shown promise in creating preferential nucleation of Li2O2 over Li2O (lithium oxide), which is irreversible with respect to lithium.[24]

Anode

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The current anode of choice in Li-air batteries is metallic Li, as Li offers the highest energy density. Due to the reactive nature of Li, the main challenge in anode development is preventing the anode from reacting. New interfacial materials or solid-state electrolytes will prevent anode degradation. Another area of concern when using metallic lithium cathodes is dendrite formation, which will lead to a short circuit within the battery.

Electrochemical

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In current cell designs, the charge overpotential is much higher than the discharge overpotential. The presence of a significant charge overpotential indicates secondary reactions, besides recharging, are occurring.[25] As a result, the electrical efficiency is only around 65%.[7] There is some indication that catalysts, such as MnO2, Co, Pt, and Au can reduce the overpotentials, but the effect is still poorly understood.[24] In addition, significant drops in cell capacity with increasing discharge rates have been observed by many researchers. The decrease in cell capacity is attributed to kinetic charge transfer limitations.[7] Since the anodic reaction occurs very quickly, the charge transfer limitations are thought to occur at the cathode. Again, electrocatalysts could improve the charge transfer rate.

Environmental

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Long term battery operation requires chemical stability of all the components of the cell. Current cell designs show poor resistance to oxidation by the reaction products and intermediates. Many aqueous electrolytes are also volatile, and can be lost over time.[7] One of the largest barriers to fully operable commercial cells is the development of effective environmental interfaces. Atmospheric oxygen is intrinsically required for cell operation, but the cell must be shielded from the environment, as water vapor can rapidly degrade the system.[1]

Applications

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The primary application for Li-air battery development is automotive. The high specific energy densities and volumetric energy densities required for next-generation hybrid and electric vehicles are beyond current battery designs. Li-air batteries are attractive for any application where weight is a primary concern, such as in mobile devices. Flow batteries, such as the vanadium redox battery may offer better performance for applications such as off-grid power storage. [26]

See Also

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The IBM Battery 500 Project

PolyPlus battery company

Lithion, Inc. Lithium-air battery design

References

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  1. ^ a b c d Ogasawara T, Debart A et al (2006). "Rechargeable Li2O2 Electrode for Lithium Batteries". Journal of American Chemical Society, 123:p.1390-1393.
  2. ^ a b Debart A, Bao,J et al (2008). "α-MnO2 Nanowires: A Catalyst for the O2 Electrode in Rechargeable Lithium Batteries",Angew.Chem.,47(24):p.4521-4524.
  3. ^ a b c d e He P, Wang Y, and Zhou H (2010). "A Li-air fuel cell with recycle aqueous electrolyte for improved stability",Electrochemistry Communications,12:p.1686-1689.
  4. ^ a b c d Kumar B, Kumar J et al (2010). "A Solid-State, Rechargeable, Long Cycle Life Lithium-Air Battery", Journal of The Electrochemical Society,157(1):A50-A54.
  5. ^ a b Wang Y, Zhou H, et al (2010). "A Lithium-Air Battery with a Potential to Continuously Reduce O2 from Air for Delivering Energy",J.Power Sources,195(1):p.358-361.
  6. ^ a b c d e f g Girishkumar G, McCloskey et al (2010). "Lithium-Air Battery: Promise and Challenges",The Journal of Physical Chemistry Letters,1:p2193-2203.
  7. ^ a b c d e f g h Kraytsberg A, Ein-Eli Y (2011). "Review on Li-air batteries - Opportunities, limitations and perspective". Journal of Power Sources,196:p.886-893.
  8. ^ a b c Abraham,KM, Jiang, Z.(1996) "A Polymer electrolyte-based rechargeable lithium/oxygen battery",Journal of the elctrochemical society,143(1):p.1-5.
  9. ^ a b c Kumar B, Kumar J (2010). " Cathodes for Solid-State Lithium-Oxygen Cells: Roles of Nasicon Glass-Ceramics",Journal of The Electrochemical Society,157(5):A611-A616.
  10. ^ a b Darren Quick (5, April 2010). "Lithium-air batteries offer three times the energy density". Retrieved 5 Oct 2011.. {{cite web}}: Check date values in: |accessdate= and |date= (help)
  11. ^ a b Shimonishi A, Zhang T et al (2011). "A study on lithium/air secondary batteries-Stability of the NASICON-type lithium ion conducting solid electrolyte in alkaline aqueous solutions",Journal of Power Sources,196:p.5128-5132.
  12. ^ a b c Ed. Jurgen O. Besenhard, Handbook of Battery Materials,New Your, Wiley-VCH, 1999, ISBN:3-527-29469-4.
  13. ^ a b c Xu, K.(2004). "Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries",Chemistry Review,104(10):p.4303-4418.
  14. ^ a b Winter, M, Brodd, J.(2004)."What Are Batteries, Fuel Cells, and Supercapacitors?",Chemical Review,104(104):p.4245.
  15. ^ a b Aurbach D.(2000)."Review of selected electrode-solution interactions which determine the performance of Li and Li ion batteries",Journal of Power Sources,89(2):p.206-218.
  16. ^ a b Whittingham,M.S. (1976). "Electrical Energy Storage and Intercalation Chemistry",Science,192(4244):p1126-1127.
  17. ^ a b c d Kowalczk,I, Read,J,Salomon, M.(2007)."Li-Air Batteries: A Classic Example of Limitations Owing to Solubilities.",Pure Application Chemistry,79(5):p.851-860.
  18. ^ a b c Singh, M,Gur,I,Balsara,N.P.(2009)."Solid Electrolyte Material Manufacturable by Polymer Processing Methods",U.S. Patent Application,#12271829.
  19. ^ a b Bates,J.B, Dudney, N.J.Evans,C.D. et al(2000)."Thin-Film Lithium and Lithium-Ion Batteries",Solid State Ionics,135(1-4):p.33-45.
  20. ^ a b Visco,S.J,Nimonm,Y,S.(2010)."Active Metal/Aqueous Electrochemical Cells and Systems",U.S.Patent,#7645543.
  21. ^ a b New Energy and Fuel.2011.WordPress.20 Nov.2011 <http://newenergyandfuel.com>
  22. ^ a b Read,J.(2002)."Characterization of the lithium/oxygen organic electrolyte battery",..Journal of the electrochemical society,149(9):p.A1190-A1195.
  23. ^ a b Williford R.E,Zhang, J-G.(2009)."Air electrode design for sustained high power operation of Li/air batteries",Journal of power sources,194(2):p.1164-1170.
  24. ^ a b c Lu, Y.-C. et al.(2010)."The Influence of Catalysts on Discharge and Charge Voltages of Rechargeable Li-oxygen Batteries",Electrochemical and Solid State Letters,13:p.A69-A72.
  25. ^ a b Zhang, T. et al.(2010)."A novel high energy density rechargeable lithium/air battery",Chem. Commun.,46:p.1661-1663.
  26. ^ a b Fabjan, Ch. et al.(2001)."The vanadium redox battery: an efficient storage unit for photovoltaic systems",Electrochemica Acta,47:p.825-831.
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