A high-capacity lithium–air battery with Pd modified carbon nanotube sponge cathode working in regular air Yue Shen a,1 , Dan Sun a,1 , Ling Yu a , Wang Zhang a , Yuanyuan Shang b , Huiru Tang c , Junfang Wu c , Anyuan Cao b, * , Yunhui Huang a, * a State Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan, Hubei 430074, China b Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing 100871, China c State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, China ARTICLE INFO Article history: Received 8 February 2013 Accepted 29 May 2013 Available online 13 June 2013 ABSTRACT We report a lithium–air battery with a free-standing, highly porous Pd-modified carbon nanotube (Pd–CNT) sponge cathode. The Pd-CNT sponge was synthesized through a chem- ical vapor deposition growth followed with an electrochemical deposition process. To build a whole lithium–air battery, the air cathode is integrated with a ceramic electrolyte-pro- tected lithium metal anode and non-volatile ionic liquid electrolyte. The lithium anode is stable during the operation and long-time storage and the ionic liquid is chemically inert. By controlling the amount of ionic liquid electrolyte, the sponge is wet but not fulfilled by the electrolyte. Such configuration offers a tricontinuous passage for lithium ions, oxygen and electrons, which is propitious to the discharge reaction. In addition, the existence of Pd nanoparticles improves the catalytic reactivity of the oxygen reduction reaction. The bat- tery is durable to any humidity level and delivers a capacity as high as 9092 mA h g 1 . Ó 2013 Elsevier Ltd. All rights reserved. 1. Introduction The lithium–air battery is receiving world-wide interest be- cause its theoretical specific energy far exceeds the best of lithium-ion batteries [1–5]. By carefully designing the porosity, conductivity and catalytic reactivity of the air cathode, the cathode capacity of the lithium–air battery with organic elec- trolyte can reach 15 000 mA h g 1 [6]. However, the lithium–air battery is still far from practical application due to a lot of problems such as low discharge rate, poor cyclability and rigorous operation condition [7]. Most of the organic electrolyte lithium–air batteries have to be operated in pure oxygen atmosphere to avoid the fast oxidation of the lithium anode in humid air [8–12]. Aqueous electrolyte lithium–air batteries with ceramic electrolyte (lithium super ionic con- ductor, LiSICON [13]) protected anode have been developed to overcome this disadvantage [14–20]. Nevertheless, the en- ergy density of an aqueous electrolyte battery is much lower than the organic electrolyte system [21]. And the evaporation of the aqueous electrolyte in open air condition is always a problem. All solid-state lithium–air battery with LiSICON powder as the cathode electrolyte is an optional choice [22,23], but the ionic conductivity at the grain boundary of the LiSICON powder is usually too low. Obtaining high 0008-6223/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.carbon.2013.05.066 * Corresponding authors: Fax: +86 27 87558241 (Y. Huang). E-mail address: [email protected](Y. Huang). 1 These authors contributed equally to this work. CARBON 62 (2013) 288 – 295 Available at www.sciencedirect.com journal homepage: www.elsevier.com/locate/carbon
8
Embed
A high-capacity lithium-air battery with Pd modified carbon nanotube sponge cathode working in regular air
This document is posted to help you gain knowledge. Please leave a comment to let me know what you think about it! Share it to your friends and learn new things together.
Yue Shen a,1, Dan Sun a,1, Ling Yu a, Wang Zhang a, Yuanyuan Shang b, Huiru Tang c,Junfang Wu c, Anyuan Cao b,*, Yunhui Huang a,*
a State Key Laboratory of Material Processing and Die & Mould Technology, School of Materials Science and Engineering,
Huazhong University of Science and Technology, Wuhan, Hubei 430074, Chinab Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing 100871, Chinac State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics,
Chinese Academy of Sciences, Wuhan 430071, China
A R T I C L E I N F O A B S T R A C T
Article history:
Received 8 February 2013
Accepted 29 May 2013
Available online 13 June 2013
We report a lithium–air battery with a free-standing, highly porous Pd-modified carbon
nanotube (Pd–CNT) sponge cathode. The Pd-CNT sponge was synthesized through a chem-
ical vapor deposition growth followed with an electrochemical deposition process. To build
a whole lithium–air battery, the air cathode is integrated with a ceramic electrolyte-pro-
tected lithium metal anode and non-volatile ionic liquid electrolyte. The lithium anode is
stable during the operation and long-time storage and the ionic liquid is chemically inert.
By controlling the amount of ionic liquid electrolyte, the sponge is wet but not fulfilled by
the electrolyte. Such configuration offers a tricontinuous passage for lithium ions, oxygen
and electrons, which is propitious to the discharge reaction. In addition, the existence of Pd
nanoparticles improves the catalytic reactivity of the oxygen reduction reaction. The bat-
tery is durable to any humidity level and delivers a capacity as high as 9092 mA h g�1.
� 2013 Elsevier Ltd. All rights reserved.
1. Introduction
The lithium–air battery is receiving world-wide interest be-
cause its theoretical specific energy far exceeds the best of
lithium-ion batteries [1–5]. By carefully designing the porosity,
conductivity and catalytic reactivity of the air cathode, the
cathode capacity of the lithium–air battery with organic elec-
trolyte can reach 15000 mA h g�1 [6]. However, the lithium–air
battery is still far from practical application due to a lot of
problems such as low discharge rate, poor cyclability and
rigorous operation condition [7]. Most of the organic
electrolyte lithium–air batteries have to be operated in pure
oxygen atmosphere to avoid the fast oxidation of the lithium
anode in humid air [8–12]. Aqueous electrolyte lithium–air
batteries with ceramic electrolyte (lithium super ionic con-
ductor, LiSICON [13]) protected anode have been developed
to overcome this disadvantage [14–20]. Nevertheless, the en-
ergy density of an aqueous electrolyte battery is much lower
than the organic electrolyte system [21]. And the evaporation
of the aqueous electrolyte in open air condition is always a
problem. All solid-state lithium–air battery with LiSICON
powder as the cathode electrolyte is an optional choice
[22,23], but the ionic conductivity at the grain boundary of
the LiSICON powder is usually too low. Obtaining high
of Pd effectively improves its catalytic activity. When Pd–
CNT sponge is wetted with an ionic liquid electrolyte and
integrated with a ceramic electrolyte protected Li–metal an-
ode, the battery can tolerate regular air with any humidity le-
vel and delivers a capacity as high as 9092 mA h g�1. Our
results indicate a promising way to achieve practically usable
lithium–air batteries with high capacity.
Acknowledgements
We acknowledge financial supports from the China Postdoc-
toral Science Foundation (2012M510178), Natural Science
Foundation of China (51202076, 20825520) and Ministry of Sci-
ence and Technology of China (2011YQ12003503). The authors
thank Analytical and Testing Center of HUST for XRD and
SEM measurements. A. Cao acknowledges financial support
from the Beijing Natural Science Foundation (Program No.
8112017) and Prof. Dehai Wu and Kunlin Wang for help in pre-
paring carbon nanotube sponge samples.
R E F E R E N C E S
[1] Abraham KM, Jiang Z. A polymer electrolyte-basedrechargeable lithium/oxygen battery. J. Electrochem. Soc.1996;143(1):1–5.
[2] Christensen J, Albertus P, Sanchez-Carrera RS, Lohmann T,Kozinsky B, Liedtke R, et al. A critical review of Li/airbatteries. J. Electrochem. Soc. 2012;159(2):R1–R30.
[3] Bruce PG, Freunberger SA, Hardwick LJ, Tarascon J-M. Li–O(2)and Li–S batteries with high energy storage. Nat. Mater.2012;11(1):19–29.
[4] Lee J-S, Kim ST, Cao R, Choi N-S, Liu M, Lee KT, et al. Metal–air batteries with high energy density: Li–air versus Zn–air.Adv. Energy Mater. 2011;1(1):34–50.
[5] Kraytsberg A, Ein-Eli Y. Review on Li–air batteries –opportunities, limitations and perspective. J. Power Sources2011;196(3):886–93.
[6] Xiao J, Mei D, Li X, Xu W, Wang D, Graff GL, et al.Hierarchically porous graphene as a lithium–air batteryelectrode. Nano Lett. 2011;11(11):5071–8.
[7] Padbury R, Zhang X. Lithium–oxygen batteries-limitingfactors that affect performance. J. Power Sources2011;196(10):4436–44.
[8] Sun B, Wang B, Su D, Xiao L, Ahn H, Wang G. Graphenenanosheets as cathode catalysts for lithium–air batterieswith an enhanced electrochemical performance. Carbon2012;50(2):727–33.
[9] Oh SH, Black R, Pomerantseva E, Lee J-H, Nazar LF. Synthesisof a metallic mesoporous pyrochlore as a catalyst forlithium–O2 batteries. Nat. Chem. 2012;4(12):1004–10.
[10] Jung H-G, Hassoun J, Park J-B, Sun Y-K, Scrosati B. Animproved high-performance lithium–air battery. Nat. Chem.2012;4(7):579–85.
[12] Zhang L, Zhang X, Wang Z, Xu J, Xu D, Wang L. High aspectratio gamma-MnOOH nanowires for high performancerechargeable nonaqueous lithium–oxygen batteries. Chem.Commun. 2012;48(61):7598–600.
[13] Fu J. Superionic conductivity of glass–ceramics in the systemLi2O–Al2O3–TiO2–P2O5. Solid State Ionics 1997;96(3–4):195–200.
[14] Zhang T, Imanishi N, Shimonishi Y, Hirano A, Takeda Y,Yamamoto O, et al. A novel high energy density rechargeablelithium/air battery. Chem. Commun. 2010;46(10):1661–3.
[15] Zhang T, Imanishi N, Takeda Y, Yamamoto O. Aqueouslithium/air rechargeable batteries. Chem. Lett.2011;40(7):668–73.
[16] Zhang T, Imanishi N, Hirano A, Takeda Y, Yamamoto O.Stability of Li/polymer electrolyte-ionic liquid composite/lithium conducting glass ceramics in an aqueous electrolyte.Electrochem. Solid-State Lett. 2011;14(4):A45–8.
[17] He P, Wang Y, Zhou H. Titanium nitride catalyst cathode in aLi–air fuel cell with an acidic aqueous solution. Chem.Commun. 2011;47(38):10701–3.
[18] Li L, Zhao X, Manthiram A. A dual-electrolyte rechargeableLi–air battery with phosphate buffer catholyte. Electrochem.Commun. 2012;14(1):78–81.
[19] Zhou H, Wang Y, Li H, He P. The development of a new type ofrechargeable batteries based on hybrid electrolytes.ChemSusChem 2010;3(9):1009–19.
[20] Wang Y, Zhou H. A lithium–air battery with a potential tocontinuously reduce O2 from air for delivering energy. J.Power Sources 2010;195(1):358–61.
[21] Zheng JP, Andrei P, Hendrickson M, Plichta EJ. The theoreticalenergy densities of dual-electrolytes rechargeable Li–air andLi–air flow batteries. J. Electrochem. Soc. 2011;158(1):A43–6.
[22] Kitaura H, Zhou H. Electrochemical performance of solid-state lithium–air batteries using carbon nanotube catalyst inthe air electrode. Adv. Energy Mater. 2012;2(7):889–94.
[23] Kumar B, Kumar J, Leese R, Fellner JP, Rodrigues SJ, AbrahamKM. A solid-state, rechargeable, long cycle life lithium–airbattery. J. Electrochem. Soc. 2010;157(1):A50–4.
[24] Zhang T, Zhou H. From Li–O2 to Li–air batteries: carbonnanotubes/ionic liquid gels with a tricontinuous passage ofelectrons, ions, and oxygen. Angew. Chem. Int. Ed.2012;51(44):11062–7.
[25] Gui X, Wei J, Wang K, Cao A, Zhu H, Jia Y, et al. Carbonnanotube sponges. Adv. Mater. 2010;22(5):617–21.
[26] Hu L, Wu H, Gao Y, Cao A, Li H, McDough J, et al. Silicon–carbon nanotube coaxial sponge as Li–ion anodes with highareal capacity. Adv. Energy Mater. 2011;1(4):523–7.
[27] Chen Y, Freunberger SA, Peng Z, Barde F, Bruce PG. Li–O2battery with a dimethylformamide electrolyte. J. Am. Chem.Soc. 2012;134(18):7952–7.
[28] Freunberger SA, Chen Y, Drewett NE, Hardwick LJ, Barde F,Bruce PG. The lithium–oxygen battery with ether-basedelectrolytes. Angew. Chem. Int. Ed. 2011;50(37):8609–13.
[29] Freunberger SA, Chen Y, Peng Z, Griffin JM, Hardwick LJ, BardeF, et al. Reactions in the rechargeable Lithium–O2 batterywith alkyl carbonate electrolytes. J. Am. Chem. Soc.2011;133(20):8040–7.
[30] Peng Z, Freunberger SA, Chen Y, Bruce PG. A reversible andhigher-rate Li–O2 battery. Science 2012;337(6094):563–6.
[31] Lim H-D, Park K-Y, Gwon H, Hong J, Kim H, Kang K. Thepotential for long-term operation of a lithium–oxygen batteryusing a non-carbonate-based electrolyte. Chem. Commun.2012;48(67):8374–6.
[32] Xu D, Wang ZL, Xu JJ, Zhang LL, Zhang XB. Novel DMSO-basedelectrolyte for high performance rechargeable Li–O-2batteries. Chem. Commun. 2012;48(55):6948–50.
[33] Yoo E, Zhou H. Li–air rechargeable battery based on metal-free graphene nanosheet catalysts. ACS Nano2011;5(4):3020–6.