Lithium Air Battery: Alternate Energy Resource For The Future
Lithium Air Battery: Alternate Energy Resource For The Future
Lithium Air Battery: Alternate Energy Resource For The Future
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ABSTRACT :
Increasing demand of energy, the depletion of fossil fuel reserves, energy security and the climate
change have forced us to look upon alternate energy resources. For today’s electric vehicles that run
on lithium-ion batteries, one of the biggest downsides is the limited range between recharging. Over
the past several years, researchers have been working on lithium–air battery. These batteries could
significantly increase the range of electric vehicles due to their high energy density, which could
theoretically be equal to the energy density of gasoline. Li-air batteries are potentially viable ultra-
high energy density chemical power sources, which could potentially offer specific energies up to
3000 Whkg−1 being rechargeable. This paper provides a review on Lithium air battery as alternate
energy resource for the future.
Keywords: Porous air cathode, Catalyst, Lithium air battery, Electrolyte, Energy storage
Received March 3, 2012 : Accepted March 27, 2012
trolyte to meet with oxygen at cathode and forms et al.1) was the first to suggest the following reaction
water as a product which is not stored in the cell but in mechanism:
lithium air battery lithium ions moves through electro-
lyte and meet with oxygen at air cathode which is nor- Li + 1--- O 2 → 1--- Li 2 O 2 (1)
2 2
mally obtained from air and forms Lithium oxide
which is accumulated inside the porous electrode. The Li + 1--- O 2 → 1--- Li 2 O (2)
4 2
major difference between the two is that for lithium air
battery an open system is required for the oxygen and The reversible cell voltage is Eo = 3.10 V for the
as well as dehydration membrane3,4) because lithium reaction (1) and Eo = 2.91 V for reaction (2). The stan-
metal is very sensitive to moisture and aggressively dard cell potentials were calculated by using the stan-
reacts with water. dard Gibbs free energy of formation. Lu et al. 18)
reported the reversible cell voltages according to the
2. Working Principle and the Electrochem- following equations:
ical Reactions of Lithium Air Batteries
2Li + O 2 → Li2 O 2 (3)
As we know during discharge, lithium ions dissolve
from the surface of the lithium metal anode and trans- 4Li + O 2 → 2Li 2 O (4)
fer to the cathode through the electrolyte and during
charge, the lithium ions transfer back to the anode to The reversible cell voltage i n t hi s case i s
be back onto the surface of the lithium metal (Fig.1). Eo = 2.96 V for the reaction (3) and Eo = 2.91 V for
Lithium air batteries based on the electrolyte used reaction (4), and E is referred as Li/Li+.
can be classified into four types: (Fig. 2) Eo = −∆G/nF, where ∆G = Gibbs free energy of the
reaction, n = number of electrons transferred and
(i) Non-aqueous electrolytes F = Faraday constant.
(ii) Aqueous electrolytes Furthermore Read et al.19) and Ogasawara et al.20)
(iii) Hybrid electrolytes have introduced almost same type of reactions which
(Combination of (i) & (ii) or (iv)) are based on non-aqueous electrolytes, where each
(iv) Solid state electrolytes group have proposed some benefits and challenges of
using aprotic electrolyte.
i.e. fully aprotic or non-aqueous,5-10) aqueous10-16) Aqueous and hybrid versions of electrolytes are also
mixture of aprotic and aqueous liquid electrolytes sys- investigated by other groups to study their reaction
tem and fully solid cell with solid electrolyte system.15,17) mechanism. Polyplus21) developed the aqueous elec-
Based on non-aqueous electrolyte solvent Abraham trolyte version and Polyplus and Wang et al.22) devel-
oped hybrid electrolyte version. The hybrid electrolyte systems natural SEI is developed because the electro-
version consists of lithium metal anode, non aqueous lytes are in direct contact with the lithium metal anode.
electrolyte, super ionic conducting glass ceramic A fully solid–state Li-air battery was recently
membrane, aqueous electrolyte and the air cathode. reported by Kumar et al.23) The battery chemistry has
The fundamental reaction mechanism for both aque- been studied by various groups24,25) and is still being
ous and hybrid electrolytes are similar. The fundamen- studied by various research groups.
tal reaction mechanisms for the aqueous electrolytes All the four battery systems have their own merits
are as follows, and demerits which should be overcome to push the Li
air batteries into practical applications. Various other
+ +
2Li + 1--- O 2 + 2H → 2Li + H 2 O (5) electrolytes are discussed in detail in the following
2
sections.
(in acidic electrolyte)
efficiency was reported i.e. by using low volatility lith- tery.35) The increase in cell performance indicates that
ium air battery can be used in ambient environment. It the charge transfer resistance has been suppressed by
should be noted that the improvement in specific the nitrogen doping and the ORR oxygen reduction
capacity is attributed to the dissolution kinetics and reaction is improved. Nitrogen doping increases the
increase of oxygen solubility in TFP based electrolytes. porosity of the carbon material and the higher porosity
Less dendritic and smoother surface is reported 36) improves the higher diffusivity of oxygen in nitrogen
by using semi-interpenetrating polymer network (IPN) doped carbon which in turn enhances the cell capacity.43
structure for the protection of lithium electrode formed Generally it is assumed that the specific capacity is
by ultraviolet (UV) radiation-curing method. A curable proportional to the surface area because, larger the sur-
mixed solution consists of linear polymer (Kynar 2801 face area more the lithium oxides formed and many
dissolved in tetrahydrofuran), a crosslinking agent (1, active sites will be available for the reaction. In con-
6-Hexanediol diacrylate), liquid electrolyte (ethylene trary Yang et al.44) reported that surface area is a criti-
carbonate (EC)/propylene carbonate (PC)/1 M cal factor in the performance of air cathode and the
LiClO 4) and a photo initiator (methyl benzoylfor- specific capacity is not proportional to the surface
mate). It is suggested32) that deposition of dendritic area. Higher discharge capacity of 2500 mAh/g is
lithium can be suppressed by the introduction of the reported44) by using mesoporous mesocellular carbon
semi-IPN structure based protection. A protective foam which is about 40% more than other carbon
layer based on IPN structure37) was also formed on materials at a current density of 0.1 mA/cm2. Large
lithium electrode surface by coating a curable mixed pore volume and large mesoporous mesocellular car-
solution on lithium metal surface followed by radia- bon foam allows more lithium oxides deposit during
tion with UV light for 2 minutes and recently the discharge process.
mechanism of lithium and lithium composite anodes38) Xiao et al.45) investigated different types of carbon
are reported by Liu et al. materials for the air cathodes. On the basis of different
experimental results they reported that specific capac-
4. Lithium Air Cathode Characteristics ity is proportional to the mesopore volume of the car-
bon materials. Electrolyte filling is another important
Lithium air cathode is almost similar to that of a fuel factor with air cathodes because in flooded electrodes
cell cathode. Oxygen is supplied from the atmosphere oxygen gas cannot be easily diffused and mobility of
to the air cathode and reacts with lithium ions to form oxygen gas is very low in liquid phase as compared to
Li2O2 and is accumulated inside the porous cathode. In that of gaseous phase. Therefore if the electrode is
practice lithium air cathode have some serious chal- flooded with electrolyte then it leads to the poor dis-
lenges because the pores of the air cathodes are charge capacity. At constant current density the
blocked by the discharge products like lithium perox- increase in the thickness of the air electrode leads to
ide precipitates. Because of this block in the pores, the the poor electrochemical performance.46) The specific
oxygen gas and the lithium ion delivery to the internal capacity is decreased because the product is deposited
pore volume stop. There are three crucial factors such near the electrode/air interface and within the oxygen
as pore size, pore volume and surface area which can diffusion length. If the thickness of air electrode is
affect the performance and discharge capacity of the increased than oxygen diffusion length, major portion
lithium air cathode. Carbon loading is another factor of the pore volume will not be filled by the lithium
where the increase of carbon loading decreases the oxide which again leads to the decrease in specific
capacity39-42). Highest gravimetric capacity of 5813 capacity.
mAh/g is reported at a current density of 0.1 mA/cm2 Effect of oxygen pressure has also been observed by
and a carbon loading of 1.9 mg. Unfortunately the many researchers.47-49) All agrees that at high oxygen
increase of carbon loading results in the decrease in pressure the discharge capacity is increased. At low
capacity because of the block in the pores resulting in oxygen pressure the discharge product film is formed
very few pores left for oxygen flow and intercalation. on air side of the electrode which ultimately stops the
Recently it has been demonstrated that the nitrogen reaction between lithium ions and the oxygen where as
doping of the carbon materials have significantly high oxygen pressure of about 10 atm is helpful in pre-
improved the performance of the lithium oxygen bat- venting this film formation.48) Read at al.47) has con-
Journal of Electrochemical Science and Technology, Vol. 3, No. 1, 14-23 (2012) 19
cluded that the discharge capacity is proportional to Although the use of partially fluorinated solvents
the oxygen partial pressure and by using a semi–infi- reduces ionic conductivity of the liquid electrolyte, it
nite medium model with simultaneous diffusion and really enhances discharge performance of Li/air cells,
reaction discharge capacity can be increased. The including both specific capacity and rate capability of
above mentioned fact shows that lithium air batteries the Li/air cells. Low volatility is another important
can be useful only when the partial pressure of oxygen factor on the performance of lithium air batteries, for
is higher than atmospheric pressure of oxygen which the long term operation of lithium/air batteries in
is about 0.2 atm. It is also suggested that the discharge ambient environment electrolytes should be less vola-
capacity can be increased by decreasing the electrolyte tile. Among various electrolytes, it is concluded that
viscosity. low volatile propylene carbonate (PC)/tris(2,2,2-triflu-
oroethyl) phosphate (TFP) is the best choice for the
5. Electrolytes for the Lithium Air Batteries lithium air batteries. Increased dissolution kinetics and
solubility of oxygen in TFP-containing electrolytes
Effect of non–aqueous electrolytes has been investi- leads to the better performance of lithium/air battery.
gated on the performance of lithium/air batteries by Laoire et al.8) have shown the reversible reduction of
Xu et al.50) and Zhang et al.35) Electrolytes with high O2 to long lived superoxide in a Li+ conducting elec-
polarity have ability to generate more tri–phase trolyte(LiPF6) in dimethyl sulfoxide(DMSO) for the
regions which leads to higher discharge capacity.52) It first time which gives a rational approach for the
implies that contact angle formed between the electro- selection of organic electrolyte solutions. The impor-
lyte and the air electrode has vital role on the perfor- tance of establishing the 3-phase electrochemical
mance of lithium/air batteries because of the oxygen interface in non-aqueous electrolyte is demonstrated
diffusion rate through the open channels which is sig- by creating air-diffusion paths and an air saturated por-
nificantly higher than that through the liquid electro- tion for an air cathode by Tran et al.49) A near linear
lyte. Zhang et al. 35) has reported a non–aqueous relationship between the capacity of gas diffusion
electrolyte that supports long–term operation of the Li/ electrode in a non-aqueous electrolyte and the average
air battery in dry ambient environments based on a pore diameter was demonstrated, which could be used
non–hydrolytic LiSO3CF3 salt and a low volatility pro- to estimate the capacity of the gas diffusion electrode
pylene carbonate (PC)/tris(2,2,2-trifluoroethyl) phos- quantitatively.
phate (TFP) solvent blend. They have also reported Charging process was also investigated by Xu et al.52)
that it is possible to develop a non–aqueous electrolyte by using carbonate based electrolyte. It was reported
for the operation of Li/air batteries in dry ambient that the discharged product was lithium alkyl carbon-
environments by selecting low volatile fluorinated ate and/or Li2O3 which shows that the discharge in a
compound as a co-solvent.51) carbonate based electrolyte leads to the formation of
carbonate species which causes the poor cycling effi-
ciency of lithium air batteries. The result was con-
firmed by Xiao et al.53) that discharge products from
lithium oxygen batteries are Li2CO3 and LiRCO3 when
using alkyl carbonate based electrolytes. It was
reported that when discharged at 2.0 V Li 2 CO 3 is
formed with Li2O2. It is generally assumed that the
intermediate product of the reaction between Li and
O2 is LiO2 which reacts with the carbonate solvent to
form Li2CO3 while part of the intermediate LiO2 con-
tinues to be reduced to Li 2O2 by accepting another
electron and a Li+ ion. Kuboki et al.54) reported that 1-
alkyl-3-methyl imidazolium cation and Bis [(perfluo-
Fig. 4. The effect of humidity on discharge profile. roalkyl)sulfonyl] imide anion gives the discharge
Electrolyte: 0.5M LiTFSI-EMITFSI; I: 0.01 mAcm−2; in capacity of 5360 mAh/g. Fig. 454) shows the cell tested
air.54) for 56 days in air and no significant effect of humidity
20 Awan Zahoor, Maria Christy, Yun Ju Hwang, and Kee Suk Nahm
increase the intercalation and not produce any decom- 195, 1202 (2010).
position products 18. Y. C. Lu, H. A. Gasteiger, M. C. Parent, V. Chiloyan,
• Development of porous Carbon cathodes which Y. Shao-Horn, Electrochem.Solid-State Lett., 13, A69
(2010).
are not contaminated by discharge products or mois-
19. J. Read, J. Electrochem. Soc., 153(1), A96 (2006).
turized due to the atmospheric gases etc., 20. T. Ogasawara, A. Debart, M. Holzapfel, P. Novakand,
• Development of a new catalyst for long cycle life, and P. G. Bruce, J. Am. Chem. Soc., 128, 1390 (2006).
cycle efficiency and to control the redox process. 21. S. J. Visco, and Y. S. Nimon, US Patent, 7, 645, 543
(2010).
Acknowledgement 22. Y. Wang, and H. Zhou, J. Power Sources, 195, 358 (2010).
23. B. Kumar, J. Kumar, R. Leese, J. P. Fellner, S. J.
Rodrigues, and K. M. Abraham, J. Electrochem. Soc.,
This work was supported by New & Renewable
157(1), A50 (2010).
Energy R&D program (2009T100100606) under the 24. S. Rajendran, and T. Uma, Mater. Lett. 44, 208 (2000).
Ministry of Knowledge Economy, Republic of Korea. 25. S. Rajendran, P. Sivakumar, R.S. BABU Bull. Mater. Sci.,
29(7), 673 (2006).
References 26. R. C. Agrawal, and G. P. Pandey, J. Phys. D: Appl.
Phys. 41, 223001(2008).
1. K. M. Abraham, and Z. Jiang, J. Electrochem. Soc.,143, 27. G. Y. Aleshin, D. A. Semenenko, A. I. Belova, T. K.
1(1996). Zakharchenko, D. M. Itkis, E. A. Goodilin, and Y. D.
2. J. Read, J. Electrochem. Soc., 149, A1190 (2002). retyakov, Solid State Ionics, 184(1), 62 (2011).
3. J. A. Zhang, W. Xu, X. H. Li, and W. Liu, 28. H. Ota, K. Shima, M. Ue, and J-ichi Yamaki
J. Electrochem. Soc., 157 , A940 (2010). Electrochimica Acta, 49, 565 (2004).
4. J. G. Zhang, D. Y. Wang, W. Xu, J. Xiao, and R. E. 29. A. A. Arie, and J. K. Lee, Diamond & Related Materials,
Williford, J. Power Sources, 195 , 433 (2010). 20, 403 (2011).
5. D. Vasudevan, and H. Wendt, J Electroanal. Chem. 392, 30. S. J. Visco, and Y. S. Nimon, U.S. Patent, 7, 282, 295
69 (1995). (2007).
6. D. L. Maricle, and W. G. Hodgson, Anal Chem 37, 1562 31. M. Ishikawa, S. Machino, M. Morita, J. Electroanal.
(1965). Chem., 473, 279 (1999).
7. M. E. Peover, and B. S. White, Chem Commun 183(1965). 32. S. Shiraishi, K. Kanamura, and Z. I. Takehara, J. Appl.
8. C. O. Laoire, S. Mukerjee, K. M. Abraham, E. J. Plichta, Electrochem., 29, 869 (1999).
and M. A. Hendrickson, J Phys Chem C 114, 9178 33. K. Kanamura , H. Tomura , S. Shiraishi , Z. I. Takehara ,
(2010). J. Electrochem. Soc., 142, 340 (1995).
9. Z. Peng, S. A. Freunberger, L. J. Hardwick, Y. Chen, 34. T. Osaka, M. kitahara, Y. Uchida, T. Momma, K. Nishimura,
V. Giordani, F. Bard, P. Novk, D. Graham, J. M. Tarascon, J. Power Sources, 81-82, 734 (1999).
and P. G. Bruce, Angew Chem Int Ed 50, 6351(2011). 35. S. S. Zhang, K. Xu, and J. Read, J. Power Sources, 196,
10. I. Kowalczk, J. Read, and M. Salomon, Pure Appl. 3906 (2011).
Chem., 79(5), 851(2007). 36. N. S. Choi, Y. M. Lee, W. Seol, J. A. Lee, and J. K. Park,
11. B. Meyer, M. Salomon, and D. Foster. Electrospun Solid State Ionics, 172, 19 (2004).
Membranes for Li-Ion Batteries, Abstract 119, presented 37. N. S. Choi, Y. M. Lee, K. Y. Cho, D. H. Ko, and J. K.
at the 209th meeting of the Electrochemical Society, Park, Electrochem. Comm., 6, 1238 (2004).
Denver, CO, 7-12 May (2006). 38. X. Liu, M. Zheng, and K. Xie, J. Power Sources 196,
12. MaxPower program on Ambient Temperature Li-Based 10667 (2011).
Reserve Batteries, U.S. Army Contract No. W911QX-05- 39. S. D. Beattle, D. M. Manolescu, and S. Blair,
C-011. J. Electrochem. Soc. 156(1), A44 (2009).
13. J. Fu, U.S. Patent 6, 485, 622, November 26, (2002) and 40. M. Wang, Y. Yang, and Y. Zhang, Nanoscale, 3, 4434
earlier patents cited therein. (2011).
14. Alupower, Inc. Electrochemical Cathode and Materials 41. S. Yang, X. Wang, X. Yang, Z. Liu, Q. Wei, and H. Shu,
Therefore, U.S. Patent 5,053,375, October 1, (1991.) International Journal of Electrochemistry, 2012, Article
15. S. Hasegawa, N. Imanishi, T. Zhang, J. Xie, A. Hirano, ID 323560, 9 (2012).
Y. Takeda, and O. Yamamoto, J. Power Sources, 189, 42. Z. Chen, D. J. Lee, Y. K. Sun, and K. Amine, MRS
371 (2009). Bulletin, 36, 498 (2011).
16. T. Zhang, N. Imanishi, S. Hasegavwa, A. Hirano, J. Xie, Y. 43. P. Kichambare, J. Kumar, S. Rodrigues, and B. Kumar,
Takeda, O. Yamamoto, and N. Sammes, J. Electrochem. J. Power Sources, 196, 3310 (2011).
Soc., 155, A965 (2008). 44. X. H. Yang, P. He, and Y. Y. Xia, Electrochem. Comm.,
17. D. Zhang, R. Li, T. Huang, and A. Yu, J. Power Sources 11, 1127 (2009).
Journal of Electrochemical Science and Technology, Vol. 3, No. 1, 14-23 (2012) 23
45. J. Xiao, D. Wang, W. Xu, D. Wang, R. E. Williford, 56. J. W. Fergus, J. Power Sources, 195, 4554 (2010).
J. Liu, and J.G.Zhang, J.Electrochem. Soc., 157 (4), A487 57. D. Zhang, R. Li, T. Huang, and A.Yu, J. Power Sources,
(2010). 195, 1202 (2010).
46. G. Q. Zhang, J. P. Zheng, R. Liang, C. Zhang, B. Wang, 58. H. P. Zhang, P. Zhang, G. C. Li, Y. P. Wu, and D. L. Sun,
M. Hendrickson, and E. J. Plichtae, J. Electrochem. Soc., J. Power Sources, 189(1), 594 (2009).
157(8), A953 (2010). 59. P. Bonhote, P. Dias, N. Papageorgiou, K. Kalyanasundaram,
47. J. Read, K. Mutolo, M. Ervin, W. Behl, J. Wolfenstine, and M. Gratzel, Inorg. Chem., 35, 1168(1996).
A. Driedger, and D. Foster, J. Electrochem. Soc. 150, 60. X. Ren, S. S. Zhang, D. T. Tran, and J. Read, J. Mater.
A1351 (2003). Chem., 21, 10118 (2011).
48. X. H Yang and Y. Y Xia, Solid State Electrochem., 14, 61. A. Débart, A. J. Paterson, J. Bao, and P. G. Bruce, Angew
109 (2010). Chem Int Ed Engl., 47(24) 4521 (2008).
49. C. Tran, X. Q Yang, and D. Qu, J. Power Sources, 195 62. Y. Shao, S. Park, J. Xiao, J. G. Zhang, Y. Wang, and
2057 (2010). J. Liu, ACS Catal., 2, 844 (2012).
50. W. Xu, J. Xiao, D. Wang, J. Zhang and J. G. Zhang, 63. A. K.Thapa, K. Saimen, and T. Ishihara, Electrochem.
J. Electrochem. Soc., 157(2), A219 (2010). Solid-State Letters, 13 (11) A165 (2010).
51. S. S. Zhang, Journal of Power Sources, 196, 2867 64. A. K. Thapa and T. Ishihara, J.Power Sources, 196 7016
(2011). (2011).
52. W. Xu, V. V. Viswanathan, D. Wang, S. A. Towne, J. 65. G. Q. Zhang, J. P. Zheng, R. Liang, C. Zhang, B. Wang,
Xiao, Z. Nie, D. Hu, and J. G. Zhang, J. Power Sources, M. Au, M. Hendrickson, and E. J. Plichta, J. Electrochem
196, 3894 (2011). Soc., 158 (7), A822 (2011)
53. J. Xiao, J. Hu, D. Wang, D. Hu, W.Xu, G. L. Graff, 66. A. Débart, A. J. Paterson, J. Bao, and P. G. Bruce,
Z. Nie, J. Liu, and J. G. Zhang, J. Power Sources, 196, Angew. Chem., 120, 4597 (2008).
5674 (2011). 67. Y. C. Lu, Z. Xu, H. A. Gasteiger, S. Chen, K. H.
54. T. Kuboki, T. Okuyama, T. Ohsaki, and N. Takami, Schifferli, and Y.S.Horn, J. AM. CHEM. SOC., 132,
J.Power Sources, 146, 766 (2005). 12170 (2010).
55. P. Kichambare, J. Kumar, S. Rodrigues, and B. Kumar, 68. A. Débart, J. Bao, G. Armstrong, and P. G. Bruce,
J. Power Sources, 196(6), 3310 (2011). J. Power Sources, 174, 1177 (2007).