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리튬공기전지 소재 기술 개발 현황 Recent Development of Advanced Materials For Li-Air Batteries
1. 공기극 (cathode)
정 훈 기
한국과학기술연구원
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공기극 – Carbon electrode
Y. Wang and H. Zhou, Energy Environ. Sci., 2011, 4, 1704
Pencil-‐drawing on a ceramic state electrolyte Hierarchically
Porous Graphene
J.-‐G. Zhang et al., Nano LeEers, 2011, 11, 5071
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공기극 – Carbon electrode
P. G. Bruce et al., J. Am. Chem. Soc. 135 (2013) 494−500
DMSO TEGDME
TEGDME
Carbon is relaOvely stable below 3.5 V on discharge or charge (hydrophobic) but is unstable on charging above 3.5 V (in the presence of Li2O2), oxidaOvely decomposing to form Li2CO3.
DMSO
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공기극 – MnO2 catalyst
L. Trahey et al., Adv. Energy Mater. 3 (2013) 75-‐84
α-‐MnO2/ramsdellite-‐MnO2 electrode
P.G. Bruce et al., Angew. Chem. Int. Ed. 2008, 47, 4521 –4524
α-‐MnO2 Nanowires
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공기극 – Pt based catalyst
Y. Shao-‐Horn et al., J. Am. Chem. Soc., 2011, 133, 19048–19051. Y. Shao-‐Horn et al., J. Am. Chem. Soc., 2010, 132, 12170–12171
Bryan D. McCloskey et al., J. Am. Chem. Soc. 2011, 133, 18038–18041
Pt catalyzes electrolyte decomposiOon in the presence of O2.
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공기극 – Ru based catalyst
Ru and RuO2 based catalyst
H.-‐G. Jung et al., ACS Nano, 2013, 7, 3532-‐3539
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공기극 – Other Catalyst
Carbon supported TiN nanoparOcles
H. Zhou et al., Chem. Commun., 2013, 49, 1175-‐-‐1177
Co3O4 nanocrystals on graphene
Hongjie Dai et al., Nat. Mater., 2011, 10, 780-‐786
Oxide based catalyst
P.G. Bruce et al., Electrochem. Solid St. 13, A180–A183 (2010).
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공기극 – Nanoporous gold (NPG)
Y. Ding et al., Adv. Mater. 16, 1897 (2004).
P. G. Bruce et al., Science,337 (2012) 563-‐566
NPG electrode foils (dealloying white gold leaf)
Using Freestanding thin film of NPG
(Pore : 30-‐50 nm)
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리튬공기전지 소재 기술 개발 현황 Recent Development of Advanced Materials For Li-Air Batteries
2. 음 극 (Anode)
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리튬금속 음극
Highest theoretical capacity of 3,862 mAh/g (compared to graphitic carbon capacity of 370 mAh/g)
- Free from lithium intercalated cathode
Issues Dendrite formation resulting in loss of lithium, possibly a safety hazard. Solvent reduction resulting in loss of lithium and electrolyte.
Approaches Decouple lithium metal from cathode chemistry with an interphase layer stable with lithium, having good ionic conductivity and a low interfacial impedance.
- Block copolymers (Seeo) - Multiple polymer/ceramic layers (Sion Power) - Single Ion Conducting Ceramic (PolyPlus)
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The hard carbon sphere-sulfur composite cathode
Pre Lithiated Si-C composite anode
Li-Si-C/ TEGDME electrolyte/ HCS-S Lithium-Silicon-Sulfur battery
Y-.K. Sun, Journal of Power Sources, 2012 (202) 308-313
Y-.K. Sun, Journal of Power Sources, 2012 (202) 308-313
Y-.K. Sun, Journal of Power Sources, 2012 (202) 308-313
Pre lithiated Si electrode
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Performance of Li-air cell
H.-G. Jung et al. Nano Letters 12, 5775-5779 (2012).
0 200 400 600 800 1000
0.8
1.6
2.4
3.2
4.0
4.8
Vol
tage
/ V
Capacity per carbon weight / mAhg-1
1st cycle 2nd cycle 5th cycle 8th cycle 10th cycle 15th cycle
0 200 400 600 800 1000
0
1
2
3
4
5
first
first
Li/Si
Li/O2
Volta
ge /
V
Capacity / mAhg-1
Li-Metal free Air battery
Porous carbon cathode
Liquid Electrolyte
O2 O2
Lithiated Si anode
리튬금속을 사용하지 않은 리튬공기전지
