锂-空气电池正极催化剂表界面调控及构效关系研究进展

doi:10.13208/j.electrochem.180543

摘要/Abstract

摘要： 锂-空气电池被认为是最具潜力的新一代化学电源体系之一，具有能量密度高、质量轻便、可逆性高、环境污染小等优点. 但其电极上缓慢的氧还原（ORR）与氧析出（OER）动力学过程导致了能量效率降低、过电位高、循环性能差等问题，制约了锂-空气电池的发展. 双效正极催化剂的设计与开发是解决上述问题的重要途径之一. 作者通过总结近几年锂-空气电池正极催化剂的研究进展，并结合其课题组自身的工作，综述了锂-空气电池正极催化剂表界面调控及构效关系研究方面的最新进展，并展望了未来关于锂-空气电池研究的切入点，对设计、开发高效锂-空电池催化剂具有重要指导意义.

关键词: 锂-空气电池, 电催化, 表界面调控, 高能量密度, 协同效应

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.

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

中图分类号:

O646

高睿, 王俊凯, 胡中波, 刘向峰. 锂-空气电池正极催化剂表界面调控及构效关系研究进展[J]. 电化学（中英文）, 2019, 25(1): 77-88.

GAO Rui, WANG Jun-kai, HU Zhong-bo, LIU Xiang-feng. Recent Developments in Surface/Interface Modulation and Structure-Performance Relationship of Cathode Catalysts for Li-Air Batteries[J]. Journal of Electrochemistry, 2019, 25(1): 77-88.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.180543

https://electrochem.xmu.edu.cn/CN/Y2019/V25/I1/77

参考文献

[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 BaTiO_3-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 Li_2-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 La_0.6Sr_0.4Co_0.8Mn_0.2O₃ 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 La_0.6Sr_0.4Co_0.2Fe_0.8O₃ 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.