Abstract
Although the application of various nonprecious compounds as the air cathodes of Zn-air batteries has been explored, the construction of highly efficient self-supported Co-based electrodes remains challenging and highly desired given their outstanding electrocatalytic activity and cost-effectiveness. Herein, we fabricated a three-dimensional (3D) self-supported electrode based on N-doped, carbon-coated Co3O4 nanosheets grown on carbon cloth (i.e., NC-Co3O4/CC) through electrochemical deposition and carbonization. When used as a binder-free electrode for oxygen evolution reaction (OER), the NC–Co3O4/CC electrode demonstrated excellent electrocatalytic activity with an overpotential of 210 mV at 10 mA cm−2 and a Tafel slope of 79.6 mV dec−1. In the Zn-air battery test, the electrode delivered a small charge/discharge voltage gap (0.87 V at 10 mA cm−2) and exhibited high durability without degradation after 93 cycles at the large current density of 25 mA cm−2. The durability of our electrode was superior to that of a commercial Pt/C+RuO2 catalyst. The excellent performance of NC–Co3O4/CC could be attributed to the presence of 3D structures that promoted electron/ion transfer. By the absence of a binder, the carbon coating improved electron conductivity and promoted electrochemical stability. Moreover, N doping could be used to adjust the C electron structure and aeffective roccelerate electron transfer. The present study provides a facile and ute for the synthesis of various self-supported electrodes that fulfill the requirements of different energy storage and conversion devices.
摘要
多种非贵金属化合物已经被用作锌空气电池的正极材料. 钴基自支撑电极由于其制备低成本、高性能的优势而具有良好的应用前景, 但是构建高效的钴基自支撑电极仍面临很大的挑战. 本研究中, 我们采用电沉积及后续碳化的方法制备了一种在碳布上生长的氮掺杂碳包覆Co3O4纳米片三维复合材料(NC-Co3O4/CC). 作为自支撑电极用作OER催化剂, 在电流密度为10 mA cm−2时过电势为210 mV, Tafel斜率为79.6 mV dec−1. 作为锌空气电池的正极材料时, 在10 mA cm−2的电流密度下其充放电电压差为0.87 V, 即使大电流密度为25 mA cm−2时仍然具有良好的稳定性(93次循环后性能没有衰减), 远远超过了商业催化剂. NC-Co3O4/CC电极优异的性能主要归因于三维结构利于电解液离子的扩散, 同时不使用粘结剂也能够增强电极的导电性. 另外, 碳包覆不仅能够提高电子传导特性, 而且能提升电极的电化学稳定性. 氮掺杂可以调节碳的电子结构, 加速电子的传递. 本工作提供了一种简单有效的策略用于合成各种自支撑电极, 从而满足不同能量存储及转换器件对电极的需求.
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References
Liang Y, Li Y, Wang H, et al. Strongly coupled inorganic/nanocarbon hybrid materials for advanced electrocatalysis. J Am Chem Soc, 2013, 135: 2013–2036
Fu J, Cano ZP, Park MG, et al. Electrically rechargeable zinc-air batteries: progress, challenges, and perspectives. Adv Mater, 2017, 29: 1604685
Xiao Y, Tian C, Tian M, et al. Cobalt-vanadium bimetal-based nanoplates for efficient overall water splitting. Sci China Mater, 2018, 61: 80–90
Dresselhaus MS, Thomas IL. Alternative energy technologies. Nature, 2001, 414: 332–337
Yang Y, Luo M, Xing Y, et al. A universal strategy for intimately coupled carbon nanosheets/MoM nanocrystals (M = P, S, C, and O) hierarchical hollow nanospheres for hydrogen evolution catalysis and sodium-ion storage. Adv Mater, 2018, 30: 1706085
Li G, Wang X, Fu J, et al. Pomegranate-inspired design of highly active and durable bifunctional electrocatalysts for rechargeable metal-air batteries. Angew Chem Int Ed, 2016, 55: 4977–4982
Wang XR, Liu JY, Liu ZW, et al. Identifying the key role of pyridinic-N-Co bonding in synergistic electrocatalysis for reversible ORR/OER. Adv Mater, 2018, 30: 1800005
Wang Z, Jia W, Jiang M, et al. Microwave-assisted synthesis of layer-by-layer ultra-large and thin NiAl-LDH/RGO nanocomposites and their excellent performance as electrodes. Sci China Mater, 2015, 58: 944–952
Yang C, Feng J, Lv F, et al. Metallic graphene-like VSe2 ultrathin nanosheets: superior potassium-ion storage and their working mechanism. Adv Mater, 2018, 30: 1800036
Hu S, Han T, Lin C, et al. Enhanced electrocatalysis via 3D graphene aerogel engineered with a silver nanowire network for ultrahigh-rate zinc-air batteries. Adv Funct Mater, 2017, 27: 1700041
Park J, Risch M, Nam G, et al. Single crystalline pyrochlore nanoparticles with metallic conduction as efficient bi-functional oxygen electrocatalysts for Zn–air batteries. Energy Environ Sci, 2017, 10: 129–136
Chen B, He X, Yin F, et al. MO-Co@N-doped carbon (M = Zn or Co): vital roles of inactive Zn and highly efficient activity toward oxygen reduction/evolution reactions for rechargeable Zn-air battery. Adv Funct Mater, 2017, 27: 1700795
Cui Z, Fu G, Li Y, et al. Ni3FeN-supported Fe3Pt intermetallic nanoalloy as a high-performance bifunctional catalyst for metal-air batteries. Angew Chem Int Ed, 2017, 56: 9901–9905
Pei Z, Li H, Huang Y, et al. Texturing in situ: N,S-enriched hierarchically porous carbon as a highly active reversible oxygen electrocatalyst. Energy Environ Sci, 2017, 10: 742–749
Song F, Hu X. Ultrathin cobalt–manganese layered double hydroxide is an efficient oxygen evolution catalyst. J Am Chem Soc, 2014, 136: 16481–16484
Wei L, Karahan HE, Zhai S, et al. Amorphous bimetallic oxidegraphene hybrids as bifunctional oxygen electrocatalysts for rechargeable Zn-air batteries. Adv Mater, 2017, 29: 1701410
Li Y, Yin J, An L, et al. Metallic CuCo2S4 nanosheets of atomic thickness as efficient bifunctional electrocatalysts for portable, flexible Zn-air batteries. Nanoscale, 2018, 10: 6581–6588
Wu J, Ren Z, Du S, et al. A highly active oxygen evolution electrocatalyst: Ultrathin CoNi double hydroxide/CoO nanosheets synthesized via interface-directed assembly. Nano Res, 2016, 9: 713–725
Chu Y, Guo L, Xi B, et al. Embedding MnO@Mn3O4 nanoparticles in an N-doped-carbon framework derived from Mn-organic clusters for efficient lithium storage. Adv Mater, 2018, 30: 1704244
Hwang S, Meng Q, Chen PF, et al. Strain coupling of conversiontype Fe3O4 thin films for lithium ion batteries. Angew Chem Int Ed, 2017, 56: 7813–7816
Wang J, Li K, Zhong H, et al. Synergistic effect between metalnitrogen- carbon sheets and NiO nanoparticles for enhanced electrochemical water-oxidation performance. Angew Chem Int Ed, 2015, 54: 10530–10534
Wang L, Chen H, Daniel Q, et al. Promoting the water oxidation catalysis by synergistic interactions between Ni(OH)2 and carbon nanotubes. Adv Energy Mater, 2016, 6: 1600516
Wu D, Wei Y, Ren X, et al. Co(OH)2 nanoparticle-encapsulating conductive nanowires array: room-temperature electrochemical preparation for high-performance water oxidation electrocatalysis. Adv Mater, 2018, 30: 1705366
Han A, Chen H, Sun Z, et al. High catalytic activity for water oxidation based on nanostructured nickel phosphide precursors. Chem Commun, 2015, 51: 11626–11629
Fenton JL, Schaak RE. Structure-selective cation exchange in the synthesis of zincblende MnS and CoS nanocrystals. Angew Chem Int Ed, 2017, 56: 6464–6467
Yin J, Li Y, Lv F, et al. Oxygen vacancies dominated NiS2/CoS2 interface porous nanowires for portable Zn-air batteries driven water splitting devices. Adv Mater, 2017, 29: 1704681
Feng LL, Yu G, Wu Y, et al. High-index faceted Ni3S2 nanosheet arrays as highly active and ultrastable electrocatalysts for water splitting. J Am Chem Soc, 2015, 137: 14023–14026
Liu Y, Li Q, Si R, et al. Coupling sub-nanometric copper clusters with quasi-amorphous cobalt sulfide yields efficient and robust electrocatalysts for water splitting reaction. Adv Mater, 2017, 29: 1606200
Chen L, Jiang H, Hu Y, et al. In-situ growth of ultrathin MoS2 nanosheets on sponge-like carbon nanospheres for lithium-ion batteries. Sci China Mater, 2018, 61: 1049–1056
Shen H, Gracia-Espino E, Ma J, et al. Atomically FeN2 moieties dispersed on mesoporous carbon: A new atomic catalyst for efficient oxygen reduction catalysis. Nano Energy, 2017, 35: 9–16
Amiinu IS, Liu X, Pu Z, et al. From 3D ZIF nanocrystals to Co-Nx/C nanorod array electrocatalysts for ORR, OER, and Zn-air batteries. Adv Funct Mater, 2018, 28: 1704638
Cai P, Hong Y, Ci S, et al. In situ integration of CoFe alloy nanoparticles with nitrogen-doped carbon nanotubes as advanced bifunctional cathode catalysts for Zn–air batteries. Nanoscale, 2016, 8: 20048–20055
Tan P, Chen B, Xu H, et al. Co3O4 nanosheets as active material for hybrid Zn batteries. Small, 2018, 14: 1800225
Li X, Wu H, Elshahawy AM, et al. Cactus-like NiCoP/NiCo-OH 3D architecture with tunable composition for high-performance electrochemical capacitors. Adv Funct Mater, 2018, 28: 1800036
Jiang H, Liu Y, Li W, et al. Co nanoparticles confined in 3D nitrogen-doped porous carbon foams as bifunctional electrocatalysts for long-life rechargeable Zn-air batteries. Small, 2018, 14: 1703739
Xue Y, Ren Z, Xie Y, et al. CoSex nanocrystalline-dotted CoCo layered double hydroxide nanosheets: a synergetic engineering process for enhanced electrocatalytic water oxidation. Nanoscale, 2017, 9: 16256–16263
Cui Z, Li Y, Fu G, et al. Robust Fe3Mo3C supported IrMn clusters as highly efficient bifunctional air electrode for metal-air battery. Adv Mater, 2017, 29: 1702385
Meng F, Zhong H, Bao D, et al. In situ coupling of strung Co4N and intertwined N–C fibers toward free-standing bifunctional cathode for robust, efficient, and flexible Zn–air batteries. J Am Chem Soc, 2016, 138: 10226–10231
Yuan S, Huang X, Ma D, et al. Engraving copper foil to give largescale binder-free porous CuO arrays for a high-performance sodium-ion battery anode. Adv Mater, 2014, 26: 2273–2279
Qu S, Song Z, Liu J, et al. Electrochemical approach to prepare integrated air electrodes for highly stretchable zinc-air battery array with tunable output voltage and current for wearable electronics. Nano Energy, 2017, 39: 101–110
Song Z, Han X, Deng Y, et al. Clarifying the controversial catalytic performance of Co(OH)2 and Co3O4 for oxygen reduction/ evolution reactions toward efficient Zn–air batteries. ACS Appl Mater Interfaces, 2017, 9: 22694–22703
Chen X, Liu B, Zhong C, et al. Ultrathin Co3O4 layers with large contact area on carbon fibers as high-performance electrode for flexible zinc-air battery integrated with flexible display. Adv Energy Mater, 2017, 7: 1700779
Guan C, Sumboja A, Wu H, et al. Hollow Co3O4 nanosphere embedded in carbon arrays for stable and flexible solid-state zincair batteries. Adv Mater, 2017, 29: 1704117
Tang C, Wang B, Wang HF, et al. Defect engineering toward atomic Co-Nx-C in hierarchical graphene for rechargeable flexible solid Zn-air batteries. Adv Mater, 2017, 29: 1703185
Cheng H, Li ML, Su CY, et al. Cu-Co bimetallic oxide quantum dot decorated nitrogen-doped carbon nanotubes: a high-efficiency bifunctional oxygen electrode for Zn-air batteries. Adv Funct Mater, 2017, 27: 1701833
Acknowledgements
We acknowledge the support from the National Natural Science Foundation of China (21631004, 21771059 and 21571054), and Heilongjiang Provincial Postdoctoral Science Foundation (LBH-Q16194).
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Qi Liu is currently an MSc candidate in inorganic chemistry under the supervision of assistant professor Lei Wang and Prof. Honggang Fu at Heilongjiang Univesity. His research focuses on developing excellent catalyst materials of energy storage.
Lei Wang received his BSc degree in 2007 and MSc degree in 2010 from Heilongjiang University, China. In 2013, she received her PhD degree from Jilin University, China. Then, she joined Heilongjiang University as a lecturer. She became an assistant professor in 2015. Her interests focus on the carbon-based nanomaterials for Li-ion batteries, supercapacitors, fuel cells, metal-air batteries, and electrocatalysis.
Honggang Fu received his BSc degree in 1984 and MSc degree in 1987 from Jilin University, China. He joined Heilongjiang University as an assistant professor in 1988. In 1999, he received his PhD degree from Harbin Institute of Technology, China. He became a full professor in 2000. Currently, he is a Cheung Kong Scholar Professor. His interests focus on the oxide-based nanomaterials for solar energy conversion and photocatalysis, the carbon-based nanomaterials for energy conversion and storage, and electrocatalysis.
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Liu, Q., Wang, L., Liu, X. et al. N-doped carbon-coated Co3O4 nanosheet array/carbon cloth for stable rechargeable Zn-air batteries. Sci. China Mater. 62, 624–632 (2019). https://doi.org/10.1007/s40843-018-9359-7
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DOI: https://doi.org/10.1007/s40843-018-9359-7