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Corresponding Author

Xiang-feng LIU(liuxf@ucas.ac.cn)

Abstract

Lithium-air battery has been considered to be one of the most promising secondary battery systems because of its high energy density. However, the sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) on the cathode, and the high overpotential, poor cycle stability and low rate capacity have severely blocked the development and application of Li-air battery. One of the effective strategies to alleviate these issues is to develop cathode catalysts for Li-air batteries. The design and development of bifunctional cathode catalysts with high activity and efficiency on both ORR and OER is highly desired for Li-air battery.The surface or interface structure has a significant impact on the catalytic performance. In this review, the recent progress in surface/interface modulation and structure-performance relationship of the cathode catalysts for Li-air batteries is summarized. The aspects of crystal plane effect, defect engineering, and surface-interface synergetic design have all been reviewed, which also include the recent results from the authors’ group. The new lithium-air battery system based on lithium superoxide with large rate capability and ultra-low overpotential is also presented. In the last, the key issues and future perspectives are also discussed. Although great progress has been made in the research of lithium-air batteries in recent years, the foundamental scientific issues such as catalytic mechanism and electrochemical reaction mechanism are still unclear. The solution of these problems is of great importance in the design and development of high-efficiency catalysts, and in the development of lithium-air batteries. Therefore, the applications of advanced characterization and analysis techniques should be emphasized in the future research, especially in situ electrochemical characterization technology to analyze the reaction mechanism at catalyst surface/interface, as well as the formation and decomposition process of the reaction products. Combined with the electrochemical performance analysis and theoretical calculation, the mechanism of catalyst action and electrochemical reaction will be revealed, which is of great significance to promote the development of lithium-air battery.

Graphical Abstract

Keywords

lithium-air battery, electrocatalysis, surface/interface modulation, high-energy density, synergistic effect

Publication Date

2019-02-28

Online Available Date

2018-07-23

Revised Date

2018-07-10

Received Date

2018-06-19

References

[1] Lu J, Li L, Park J B, et al. Aprotic and aqueous Li-O2 batteries[J]. Chemical Reviews, 2014, 114(11): 5611-5640.
[2] Christensen J, Albertus P, Sanchez-Carrera R S, et al. A critical review of Li-air batteries[J]. Journal of The Electrochemical Society, 2012, 159(2): R1-R30.
[3] Bruce P G, Freunberger S A, Hardwick L J, et al. Li-O2 and Li-S batteries with high energy storage[J]. Nature Materials, 2012, 11(1): 19-29.
[4] Li H(李泓), Lv Y C(吕迎春). A review on electrochemical energy storage[J]. Journal of Electrochemistry(电化学), 2015, 21(5): 412-424.
[5] Li L, Chang Z W, Zhang X B. Recent rrogress on the development of metal-air batteries[J]. Advanced Sustainable Systems, 2017, 1(10): 1700036.
[6] Girishkumar G, Mccloskey B, Luntz A C, et al. Lithium-air battery: promise and challenges[J]. 2010, 1(14): 2193-2203. [7] Gittleson F S, Sekol R C, Doubek G, et al. Catalyst and electrolyte synergy in Li-O2 batteries[J]. Physical Chemistry Chemical Physics, 2014, 16(7): 3230-3237.
[8] Lim H D, Lee B, Bae Y, et al. Reaction chemistry in rechargeable Li-O2 batteries[J]. Chemical Society Reviews, 2017, 46(10): 2873-2888.
[9] Wang Y W, Wang B Z, Gu F, et al. Tuning electrochemical reactions in Li-O2 batteries[J]. Nano Advances, 2016, 1(1): 17-24.
[10] Cao R, Lee J S, Liu M L, et al. Recent progress in non-precious catalysts for metal-air batteries[J]. Advanced Energy Materials, 2012, 2(7): 816-829.
[11] Lee D U, Xu P, Cano Z P, et al. Recent progress and perspectives on bi-functional oxygen electrocatalysts for advanced rechargeable metal-air batteries[J]. Journal of Materials Chemistry A, 2016, 4(19): 7107-7134.
[12] Zhang P, Zhao Y, Zhang X B. Functional and stability orientation synthesis of materials and structures in aprotic Li-O2 batteries[J]. Chemical Society Reviews, 2018, 47(8): 2921-3004.
[13] Fu Y(付月), Wang J(王金), Yu H Y(于海洋), et al. Application of electrospinning in lithium-air batteries[J]. Journal of Electrochemistry(电化学), 2018, 24(1): 46-55.
[14] Xu S M, Liang X, Ren Z C, et al. Free-standing air cathodes based on 3D hierarchically porous carbon membranes: Kinetic overpotential of continuous macropores in Li-O2 batteries[J]. Angewandte Chemie-International Edition, 2018, 23(57): 6825-6829.
[15] Gittleson F S, Ryu W H, Schwab M, et al. Pt and Pd catalyzed oxidation of Li2O2 and DMSO during Li-O2 battery charging[J]. Chemical Communications, 2016, 52(39): 6605-6608.
[16] Chatterjee A, Or S W, Cao Y L. Transition metal hollow nanocages as promising cathodes for the long-term cyclability of Li-O2 batteries[J]. Nanomaterials(Basel, Switzerland), 2018, 8(5): DOI: 10.3390/nano8050308.
[17] Chang Y Q, Dong S M, Ju Y H, et al. A carbon- and binder-free nanostructured cathode for high-performance nonaqueous Li-O2 battery[J]. Advanced Science, 2015, 2(8): 1500092.
[18] Zhuo J L, Qing L Z, Yu W, et al. Recent progress in applying in situ/operando characterization techniques to probe the solid/liquid/gas interfaces of Li-O2 batteries[J]. Small Methods, 2017, 1(7): 1700150.
[19] Zhou K B, Li Y D. Catalysis based on nanocrystals with well-defined facets[J]. Angewandte Chemie-International Edition, 2012, 51(3): 602-613.
[20] Xie X W, Shen W J. Morphology control of cobalt oxide nanocrystals for promoting their catalytic performance[J]. Nanoscale, 2009, 1(1): 50-60.
[21] Zhou K B, Wang X, Sun X M, et al. Enhanced catalytic activity of ceria nanorods from well-defined reactive crystal planes[J]. Journal of Catalysis, 2005, 229(1): 206-212.
[22] Xie X W, Li Y, Liu Z Q, et al. Low-temperature oxidation of CO catalysed by Co3O4 nanorods[J]. Nature, 2009, 458(7239): 746-749.
[23] Tian N, Zhou Z Y, Sun S G. Platinum metal catalysts of high-index surfaces: from single-crystal planes to electrochemically shape-controlled nanoparticles[J]. Journal of Physical Chemistry C, 2008, 112(50): 19801-19817.
[24] Nicholas J F. An atlas of models of crystal surfaces[M]. gordon & breach: New York, 1965.
[25] Xiao X L, Liu X F, Zhao H, et al. Facile shape control of Co3O4 and the effect of the crystal plane on electrochemical performance[J]. Advance Materials, 2012, 24(42): 5762-5766.
[26] Gao R, Zhu J Z, Xiao X L, et al. Facet-dependent electrocatalytic performance of Co3O4 for rechargeable Li-O2 battery[J]. The Journal of Physical Chemistry C, 2015, 119(9): 4516-4523.
[27] Su D W, Dou S X, Wang G X. Single crystalline Co3O4 nanocrystals exposed with different crystal planes for Li-O2 batteries[J]. Scientific Reports, 2014, 4: 5767.
[28] Song K, Cho E, Kang Y M. Morphology and active-site engineering for stable round-trip efficiency Li-O2 batteries: a search for the most active catalytic site in Co3O4[J]. ACS Catalysis, 2015, 5(9): 5116-5122.
[29] Zhu J Z, Ren X D, Liu J J, et al. Unraveling the catalytic mechanism of Co3O4 for the oxygen evolution reaction in a Li-O2 battery[J]. ACS Catalysis, 2014, 5(1): 73-81.
[30] Zheng Y P, Song K, Jung J, et al. Critical descriptor for the rational design of oxide-based catalysts in rechargeable Li-O2 batteries: surface oxygen density[J]. Chemistry of Materials, 2015, 27(9): 3243-3249.
[31] Yan D F, Li Y X, Huo J, et al. Defect chemistry of nonprecious-metal electrocatalysts for oxygen reactions[J].Advance Materials, 2017, 29(48): 1606459.
[32] Casas-Cabanas M, Binotto G, Larcher D, et al. Defect chemistry and catalytic activity of nanosized Co3O4[J]. Chemistry of Materials, 2009, 21(9): 1939-1947.
[33] Jiang X D, Zhang Y P, Jiang J, et al. Characterization of oxygen vacancy associates within hydrogenated TiO2: A positron annihilation study[J]. The Journal of Physical Chemistry C, 2012, 116(42): 22619-22624.
[34] Lu X, Li H. Fundamental scientific aspects of lithium batteries (II)Defect chemistry in battery materials[J]. Energy Storage Science and Technology, 2013, 2(2): 157-164.
[35] Hong J H, Jin C H, Yuan J, et al. Atomic defects in two-eimensional materials: from single-atom spectroscopy to functionalities in opto-/electronics, nanomagnetism, and catalysis[J]. Advance Materials, 2017, 29(14): 1606434
[36] Chen C F, King G, Dickerson R M, et al. Oxygen-deficient BaTiO3-x perovskite as an efficient bifunctional oxygen electrocatalyst[J]. Nano Energy, 2015, 13: 423-432.
[37] Cheng F Y, Zhang T R, Zhang Y, et al. Enhancing electrocatalytic oxygen reduction on MnO2 with vacancies[J]. Angewandte Chemie-International Edition, 2013, 52(9): 2474-2477.
[38] Xu L, Jiang Q Q, Xiao Z H, et al. Plasma-engraved Co3O4 nanosheets with oxygen vacancies and high surface area for the oxygen evolution reaction[J]. Angewandte Chemie-
International Edition, 2016, 55(17): 5277-5281.
[39] Wang Y Y, Zhang Y Q, Liu Z J, et al. Layered double hydroxide nanosheets with multiple vacancies obtained by dry exfoliation as highly efficient oxygen evolution electrocatalysts[J]. Angewandte Chemie-International Edition, 2017, 56(21): 5867-5871.
[40] Gao R, Liu L, Hu Z B, et al. The role of oxygen vacancies in improving the performance of CoO as a bifunctional cathode catalyst for rechargeable Li-O2 batteries[J]. Journal of Materials Chemistry A, 2015, 3(34): 17598-17605.
[41] Gao R, Li Z Y, Zhang X L, et al. Carbon-dotted defective CoO with oxygen vacancies: A synergetic design of bifunctional cathode catalyst for Li-O2 batteries[J]. ACS Catalysis, 2015, 6(1): 400-406.
[42] Oh S H, Black R, Pomerantseva E, et al. Synthesis of a metallic mesoporous pyrochlore as a catalyst for lithium-O2 batteries[J]. Nature Chemistry, 2012, 4(12): 1004-
1010.
[43] Kang J, Kim J, Lee S, et al. Breathable carbon-free electrode: black TiO2 with hierarchically ordered porous structure for stable Li-O2 battery[J]. Advanced Energy Materials, 2017, 7(19): 1700814.
[44] Zhang S P, Wang G, Jin J, et al. Self-catalyzed decomposition of discharge products on the oxygen vacancy sites of MoO3 nanosheets for low-overpotential Li-O2 batteries[J]. Nano Energy, 2017, 36: 186-196.
[45] Wang J, Gao R, Zhou D, et al. Boosting the electrocatalytic activity of Co3O4 nanosheets for a Li-O2 battery through modulating inner oxygen vacancy and exterior Co3+/Co2+ ratio[J]. ACS Catalysis, 2017, 7(10): 6533-6541.
[46] Qu L T, Liu Y, Baek J B, et al. Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells[J]. ACS Nano, 2010, 4(3): 1321-1326.
[47] Zhang J T, Zhao Z H, Xia Z H, et al. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions[J]. Nature Nanotechnology, 2015, 10(5): 444-452.
[48] Sun B, Chen S Q, Liu H, et al. Mesoporous carbon nanocube architecture for high-performance lithium-oxygen batteries[J]. Advanced Functional Materials, 2015, 25(28): 4436-4444.
[49] Park J B, Lee J, Yoon C S, et al. Ordered mesoporous carbon electrodes for Li-O2 batteries[J]. ACS Applied Materials & Interfaces, 2013, 5(24): 13426-13431.
[50] Guo Z, Zhou D, Dong X, et al. Ordered hierarchical mesoporous/macroporous carbon: a high-performance catalyst for rechargeable Li-O2 batteries[J]. Advanced Materials, 2013, 25(39): 5668.
[51] Thotiyl M M O, Freunberger S A, Peng Z, et al. The carbon electrode in nonaqueous Li-O2 cells[J]. Journal of the American Chemical Society, 2013, 135(1): 494-500.
[52] Zhang X L, Gao R, Li Z Y, et al. Enhancing the performance of CoO as cathode catalyst for Li-O2 batteries through confinement into bimodal mesoporous carbon[J]. Electrochimica Acta, 2016, 201: 134-141.
[53] Gao R, Zhou Y, Liu X F, et al. N-Doped defective carbon layer encapsulated W2C as a multifunctional cathode catalyst for high performance Li-O2 Battery[J]. Electrochimica Acta, 2017, 245: 430-437.
[54] Xing Y, Yang Y, Chen R J, et al. Strongly coupled carbon nanosheets/molybdenum carbide nanocluster hollow nanospheres for high-performance aprotic Li-O2 battery[J]. Small, 2018,14(19): UNSP 1704366.
[55] Wang J C, Kondrat S A, Wang Y Y, et al. Au-Pd Nanoparticles dispersed on composite titania/rraphene oxide-supports as a highly active oxidation catalyst[J]. ACS Catalysis, 2015, 5(6): 3575-3587.
[56] Wang N, Sun Q M, Bai R S, et al. In situ confinement of ultrasmall Pd clusters within nanosized silicalite-1 zeolite for highly efficient catalysis of hydrogen generation[J]. Journal of the American Chemical Society, 2016, 138(24): 7484-7487.
[57] Lu Y C, Xu Z C, Gasteiger H A, et al. Platinum-gold nanoparticles: a highly active bifunctional electrocatalyst for rechargeable lithium-air batteries[J]. Journal of the American Chemical Society, 2010, 132(35): 12170-12171.
[58] Lei Y, Lu J, Luo X Y, et al. Synthesis of porous carbon supported palladium nanoparticle catalysts by atomic layer deposition: Application for rechargeable lithium-O2 battery[J]. Nano Letters, 2013, 13(9): 4182-4189.
[59] Jeong Y S, Park J B, Jung H G, et al. Study on the catalytic activity of noble metal nanoparticles on reduced graphene oxide for oxygen evolution reactions in lithium-air batteries[J]. Nano Letters, 2015, 15(7): 4261-4268.
[60] Lu J, Lee Y J, Luo X Y, et al. A lithium-oxygen battery based on lithium superoxide[J]. Nature, 2016, 529(7586): 377-382.
[61] Fan W G, Wang B Z, Guo X X, et al. Nanosize stabilized Li-deficient Li2-xO2 through cathode architecture for high performance Li-O2 batteries[J]. Nano Energy, 2016, 27: 577-586.
[62] Zhang X L, Gong Y D, Li S Q, et al. Porous perovskite La0.6Sr0.4Co0.8Mn0.2O3 nanofibers loaded with RuO2 nano-sheets as an efficient and durable bifunctional catalyst for rechargeable Li-O2 batteries[J]. ACS Catalysis, 2017, 7(11): 7737-7747.
[63] Gong Y D, Zhang X L, Li Z P, et al. Perovskite La0.6Sr0.4Co0.2Fe0.8O3 nanofibers decorated with RuO2 nanoparticles as an efficient bifunctional cathode for rechargeable Li-O2 batteries[J]. ChemNanoMat, 2017, 3(7): 485-490.
[64] Gao R, Yang Z Z, Zheng L R, et al. Enhancing the catalytic activity of Co3O4 for Li-O2 batteries through the synergy of surface/interface/doping engineering[J]. ACS Catalysis, 2018, 8(3): 1955-1963.
[65] Gao R, Liang X, Yin P G, et al. An amorphous LiO2-based Li-O2 battery with low overpotential and high rate capability[J]. Nano Energy, 2017, 41: 535-542.
[66] Zhu Z, Kushima A, Yin Z Y, et al. Anion-redox nanolithia cathodes for Li-ion batteries[J]. Nature Energy, 2016, 1: 16111.

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