Abstract
Develo** a high-efficienct, low-cost and stable non-noble-metal-based bifunctional electrocatalyst for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) as oxygen electrode material in the rechargeable zinc–air battery is crucial in renewable energy conversion technologies. In this work, nitrogen-doped hollow carbon sphere (NHCS) decorated with various nickel selenide (NixSe) nanoparticles had been designed and successfully prepared. Among them, the Ni0.85Se–NHCS with the highest percentage of Ni3+ could serve as a new efficient bifunctional electrocatalyst toward ORR/OER (with an onset potential of 0.850 V for ORR and a potential of 1.583 V at 10 mA·cm−2 for OER) in an alkaline medium. Furthermore, the assembled Zn–air battery coupled with Ni0.85Se–NHCS electrode has excellent discharging–charging performance and long lifetime. This work provides a valuable understanding on transition metal non-oxide electrocatalysts and expands the applications of selenide-based materials.
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References
Liu J, Zhu D, Zheng Y, Vasileff A, Qiao SZ (2018) Self-supported earth-abundant nanoarrays as efficient and robust electrocatalysts for energy-related reactions. ACS Catal 8:6707–6732
Liu ZQ, Cheng H, Li N, Ma TY, Su YZ (2016) ZnCo2O4 quantum dots anchored on nitrogen-doped carbon nanotubes as reversible oxygen reduction/evolution electrocatalysts. Adv Mater 28:3777–3784
Chen X, Zhou Z, Karahan HE, Shao Q, Wei L, Chen Y (2018) Recent advances in materials and design of electrochemically rechargeable zinc–air batteries. Small 14:1801929
Cheng H, Li ML, Su CY, Li N, Liu ZQ (2017) Cu–Co Bimetallic oxide quantum dot decorated nitrogen-doped carbon nanotubes: a high-efficiency bifunctional oxygen electrode for Zn–air batteries. Adv Funct Mater 27:1701833
Gu P, Zheng M, Zhao Q, **ao X, Xue H, Pang H (2017) Rechargeable zinc–air batteries: a promising way to green energy. J Mater Chem A 5:7651–7666
An L, Zhang Z, Feng J et al (2018) Heterostructure-promoted oxygen electrocatalysis enables rechargeable zinc–air battery with neutral aqueous electrolyte. J Am Chem Soc 140:17624–17631
Swesi AT, Masud J, Nath M (2016) Nickel selenide as a high-efficiency catalyst for oxygen evolution reaction. Energy Environ Sci 9:1771–1782
Guan C, Sumboja A, Wu H et al (2017) Hollow Co3O4 nanosphere embedded in carbon arrays for stable and flexible solid-state zinc–air batteries. Adv Mater 29:1704117
Singh SK, Dhavale VM, Kurungot S (2015) Surface-tuned Co3O4 nanoparticles dispersed on nitrogen-doped graphene as an efficient cathode electrocatalyst for mechanical rechargeable zinc–air battery application. ACS Appl Mater Interfaces 7:21138–21149
Su CY, Cheng H, Li W et al (2017) Atomic modulation of FeCo–nitrogen–carbon bifunctional oxygen electrodes for rechargeable and flexible all-solid-state zinc–air battery. Adv Energy Mater 7:1602420
Li Y, Zhou W, Dong J et al (2018) Interface engineered in situ anchoring of Co9S8 nanoparticles into a multiple doped carbon matrix: highly efficient zinc–air batteries. Nanoscale 10:2649–2657
Yang Y, Zhang K, Lin H, Li X, Chan HC, Yang L, Gao Q (2017) MoS2-Ni3S2 heteronanorods as efficient and stable bifunctional electrocatalysts for overall water splitting. ACS Catal 7:2357–2366
Jiang Q, Chen R, Chen H, Jiang J, Yang X, Ju Y, Ji R, Zhang Y (2018) Improved performance in dye-sensitized solar cells via controlling crystalline structure of nickel selenide. J Mater Sci 53:7672–7682. https://doi.org/10.1007/s10853-018-2065-2
Liao M, Zeng G, Luo T, ** Z, Wang Y, Kou X, **ao D (2016) Three-dimensional coral-like cobalt selenide as an advanced electrocatalyst for highly efficient oxygen evolution reaction. Electrochim Acta 194:59–66
Gong F, Wang H, Xu X, Zhou G, Wang ZS (2012) In situ growth of Co0.85Se and Ni0.85Se on conductive substrates as high-performance counter electrodes for dye-sensitized solar cells. J Am Chem Soc 134:10953–10958
Zhao Y, Zhang C, Fan R, Li J, Hao Y, He J, Alonso-Vante N, Xue J (2018) Selenium decorated reduced graphene oxide supported CoSe2 nanoparticles as efficient electrochemical catalyst for the oxygen reduction reaction. ChemElectroChem 5:3287–3292
Wang F, Li Y, Shifa TA et al (2016) Selenium-enriched nickel selenide nanosheets as a robust electrocatalyst for hydrogen generation. Angew Chem Int Ed 55:6919–6924
Ge P, Zhang C, Hou H et al (2018) Anions induced evolution of Co3X4 (X = O, S, Se) as sodium-ion anodes: the influences of electronic structure, morphology, electrochemical property. Nano Energy 48:617–629
Peng H, Ma G, Sun K, Zhang Z, Li J, Zhou X, Lei Z (2015) A novel aqueous asymmetric supercapacitor based on petal-like cobalt selenide nanosheets and nitrogen-doped porous carbon networks electrodes. J Power Sources 297:351–358
Zhang L, Sun L, Huang Y, Sun Y, Hu T, Xu K, Ma F (2017) Hydrothermal synthesis of N-doped RGO/MoSe2 composites and enhanced electro-catalytic hydrogen evolution. J Mater Sci 52:13561–13571. https://doi.org/10.1007/s10853-017-1417-7
Yuan H, Kong L, Li T, Zhang Q (2017) A review of transition metal chalcogenide/graphene nanocomposites for energy storage and conversion. Chin Chem Lett 28:2180–2194
Yu B, Hu Y, Qi F et al (2017) Nanocrystalline Ni0.85Se as efficient non-noble-metal electrocatalyst for hydrogen evolution reaction. Electrochim Acta 242:25–30
Wang H, Wang X, Yang D, Zheng B, Chen Y (2018) Co0.85Se hollow nanospheres anchored on N-doped graphene nanosheets as highly efficient, nonprecious electrocatalyst for hydrogen evolution reaction in both acid and alkaline media. J Power Sources 400:232–241
Yuan H, Jiao Q, Liu J et al (2017) Facile synthesis of Co0.85Se nanotubes/reduced graphene oxide nanocomposite as Pt-free counter electrode with enhanced electrocatalytic performance in dye-sensitized solar cells. Carbon 122:381–388
Li S, Peng S, Huang L, Cui X, Al-Enizi AM, Zheng G (2016) Carbon-coated Co3+-rich cobalt selenide derived from ZIF-67 for efficient electrochemical water oxidation. ACS Appl Mater Interfaces 8:20534–20539
Wu X, He D, Zhang H et al (2016) Ni0.85Se as an efficient non-noble bifunctional electrocatalyst for full water splitting. Int J Hydrog Energy 41:10688–10694
Ao K, Dong J, Fan C, Wang D, Cai Y, Li D, Huang F, Wei Q (2018) Formation of yolk–shelled nickel–cobalt selenide dodecahedral nanocages from metal–organic frameworks for efficient hydrogen and oxygen evolution. ACS Sustain Chem Eng 6:10952–10959
Zhang H, Yu M, Song H, Noonan O, Zhang J, Yang Y, Zhou L, Yu C (2015) Self-Organized mesostructured hollow carbon nanoparticles via a surfactant-free sequential heterogeneous nucleation pathway. Chem Mater 27:6297–6304
Létiche M, Brousse K, Demortière A et al (2017) Sputtered titanium carbide thick film for high areal energy on chip carbon-based micro-supercapacitors. Adv Funct Mater 27:1606813
Tan L, Yang YD, Li N, Chen S, Liu ZQ (2017) Enhanced activity and stability of Co3O4-decorated nitrogen-doped carbon hollow sphere catalysts for microbial fuel cells. Catal Sci Technol 7:1315–1323
Zhang J, Zhang C, Li W et al (2018) Nitrogen-doped perovskite as a bifunctional cathode catalyst for rechargeable lithium–oxygen batteries. ACS Appl Mater Interfaces 10:5543–5550
Zheng X, Han X, Liu H et al (2018) Controllable synthesis of NixSe (0.5 < x < 1) Nanocrystals for efficient rechargeable zinc–air batteries and water splitting. ACS Appl Mater Interfaces 10:13675–13684
Liu X, Zhai ZY, Chen Z, Zhang LZ, Zhao XF, Si FZ, Li JH (2018) Engineering mesoporous NiO with enriched electrophilic Ni3+ and O− toward efficient oxygen evolution. Catalysts 8:310
Tang C, Cheng N, Pu Z, **ng W, Sun X (2015) NiSe Nanowire film supported on nickel foam: an efficient and stable 3D bifunctional electrode for full water splitting. Angew Chem Int Ed 54:9351–9355
Liu J, Zheng Y, Jiao Y, Wang Z, Lu Z, Anthony V, Qiao S (2018) NiO as a bifunctional promoter for RuO2 toward superior overall water splitting. Small 14:1704073
Liu J, Zhu D, Ling T, Anthony V, Qiao S (2017) S-NiFe2O4 ultra-small nanoparticle built nanosheets for efficient water splitting in alkaline and neutral pH. Nano Energy 40:264–273
Wang HY, Hsu YY, Chen R, Chan TS, Chen HM, Liu B (2015) Ni3+-Induced formation of active NiOOH on the spinel Ni–Co oxide surface for efficient oxygen evolution reaction. Adv Energy Mater 5:1500091
Tian GL, Zhao MQ, Yu D, Kong XY, Huang JQ, Zhang Q, Wei F (2014) Nitrogen–doped graphene/carbon nanotube hybrids: in situ formation on bifunctional catalysts and their superior electrocatalytic activity for oxygen evolution/reduction reaction. Small 10:2251–2259
Wang HF, Tang C, Wang B, Li BQ, Zhang Q (2017) Bifunctional transition metal hydroxysulfides: room-temperature sulfurization and their applications in Zn–air batteries. Adv Mater 29:1702327
Tian T, Gao H, Zhou X, Zheng L, Wu J, Li K, Ding Y (2018) Study of the active sites in porous nickel oxide nanosheets by manganese modulation for enhanced oxygen evolution catalysis. ACS Energy Lett 3:2150–2158
Huang Y, Chong X, Liu C, Liang Y, Zhang B (2018) Boosting hydrogen production by anodic oxidation of primary amines over a NiSe nanorod electrode. Angew Chem Int Ed 130:13347–13350
Chaudhari NK, ** H, Kim B, Lee K (2017) Nanostructured materials on 3D nickel foam as electrocatalysts for water splitting. Nanoscale 9:12231–12247
Acknowledgements
This study was funded by Guangzhou municipal Science and Technology Project (No.201607010263), Featured Innovation Project of Guangdong Universities (No. 2017KTSCX142), Undergraduate’s Innovation Training Program (No. 201711078005), and “Climbing” Program of Undergraduate of Guangdong Province (No. pdjh2019b0388).
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Pan, QR., Li, SJ., Tong, K. et al. Engineering Ni3+ inside nickel selenide as efficient bifunctional oxygen electrocatalysts for Zn–air batteries. J Mater Sci 54, 9063–9074 (2019). https://doi.org/10.1007/s10853-019-03520-w
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DOI: https://doi.org/10.1007/s10853-019-03520-w