SCIENCE CHINA Materials, Volume 60, Issue 10: 947-954(2017) https://doi.org/10.1007/s40843-017-9094-5

Fabrication of multifunctional carbon encapsulated Ni@NiO nanocomposites for oxygen reduction, oxygen evolution and lithium-ion battery anode materials

More info
  • ReceivedJun 15, 2017
  • AcceptedAug 7, 2017
  • PublishedSep 6, 2017


Multifunctional carbon encapsulated Ni@NiO nanocomposites (Ni@NiO@C) were synthesized for applications in oxygen reduction reactions (ORR), oxygen evolution reactions (OER) and lithium-ion batteries (LIB). The morphology was investigated via SEM and TEM, suggesting that the Ni@NiO@C nanocomposites have uniform and spherical core-shell structures. When the Ni@NiO@C nanocomposite is used as the catalyst in ORR, 90% of the initial current density can be maintained after 15 h in O2-saturated 0.1 mol L−1 KOH at 0.3 V under a rotation speed of 1600 rpm. As a catalyst for OER, the highest activity overpotential of the Ni@NiO@C nanocomposite electrocatalyst is 380 mV (vs. RHE) under the current density of 10 mA cm−2, and the Tafel slope was calculated to be 55 mV dec−1 by linear fitting. Electrochemical performances of the Ni@NiO@C nanocomposites used as LIB electrodes exhibited a long cycling life with a high capacity of 750 mA h g−1 after 400 cycles under 200 mA g−1.

Funded by

This work was supported by the National Natural Science Foundation of China (51571172,51672240,51571171,11404280)

Natural Science Foundation for Distinguished Young Scholars of Hebei Province(E2017203095)

Natural Science Foundation of Hebei Province(E2016203484,A2015203337)

Research Program of the College Science & Technology of Hebei Province(ZD2017083,QN2014047)


This work was supported by the National Natural Science Foundation of China (51571172, 51672240, 51571171, and 11404280), the Natural Science Foundation for Distinguished Young Scholars of Hebei Province (E2017203095), the Natural Science Foundation of Hebei Province (E2016203484 and A2015203337), and the Research Program of the College Science & Technology of Hebei Province (ZD2017083 and QN2014047).

Interest statement

The authors declare that they have no conflict of interest.

Contributions statement

Xu D performed the experiments with help from Ruan W and Du X. Mu C wrote the manuscript with support from Wang B, Xiang J and Tian Y. Wen F and Liu Z conceived the research. All authors contributed to the general discussion.

Author information

Dongyang Xu was born in 1991. He received his Master’s degree in material physics from Yanshan University in 2017. His research interest focuses on the synthesis and application of porous carbon parcel metal and its oxide materials for the energy storage and electrochemical catalysis.

Congpu Mu was born in 1984 and joined Yanshan University in 2013. He completed his PhD in physics at Lanzhou University in 2013. His research is related to magnetic nanomaterials, from magnetic metals to magnetic oxide with their applications in microwave absorption and energy storage.


Supplementary information

Supporting data are available in the online version of the paper.


[1] Wang H, Zhang X. Designing multi-shelled metal oxides: towards high energy-density lithium-ion batteries. Sci China Mater, 2016, 59: 521-522 CrossRef Google Scholar

[2] Gao MR, Xu YF, Jiang J, et al. Nanostructured metal chalcogenides: synthesis, modification, and applications in energy conversion and storage devices. Chem Soc Rev, 2013, 42: 2986-3017 CrossRef PubMed Google Scholar

[3] Lewandowicz G, Jankowski T, Fornal J. Effect of microwave radiation on physico-chemical properties and structure of cereal starches. Carbohydrate Polymers, 2000, 42: 193-199 CrossRef Google Scholar

[4] Zhang G, Xu Y, Wang L, et al. Rational design of graphene oxide and its hollow CoO composite for superior oxygen reduction reaction. Sci China Mater, 2015, 58: 534-542 CrossRef Google Scholar

[5] Zhao R, Xia W, Lin C, et al. A pore-expansion strategy to synthesize hierarchically porous carbon derived from metal-organic framework for enhanced oxygen reduction. Carbon, 2017, 114: 284-290 CrossRef Google Scholar

[6] Liu M, Steven Tay NH, Bell S, et al. Review on concentrating solar power plants and new developments in high temperature thermal energy storage technologies. Renew Sustain Energ Rev, 2016, 53: 1411-1432 CrossRef Google Scholar

[7] Xu D, Mu C, Xiang J, et al. Carbon-encapsulated Co3O4@CoO@Co nanocomposites for multifunctional applications in enhanced long-life lithium storage, supercapacitor and oxygen evolution reaction. Electrochim Acta, 2016, 220: 322-330 CrossRef Google Scholar

[8] Zhang X, Xiang J, Mu C, et al. SnS2 nanoflakes anchored graphene obtained by liquid phase exfoliation and MoS2 nanosheet composites as lithium and sodium battery anodes. Electrochim Acta, 2017, 227: 203-209 CrossRef Google Scholar

[9] Liang C, Li Z, Dai S. Mesoporous carbon materials: synthesis and modification. Angew Chem Int Ed, 2008, 47: 3696-3717 CrossRef PubMed Google Scholar

[10] Frackowiak E, Béguin F. Carbon materials for the electrochemical storage of energy in capacitors. Carbon, 2001, 39: 937-950 CrossRef Google Scholar

[11] Balandin AA. Thermal properties of graphene and nanostructured carbon materials. Nat Mater, 2011, 10: 569-581 CrossRef PubMed ADS Google Scholar

[12] Zhang T, He C, Sun F, et al. Co3O4 nanoparticles anchored on nitrogen-doped reduced graphene oxide as a multifunctional catalyst for H2O2 reduction, oxygen reduction and evolution reaction. Sci Rep, 2017, 7: 43638 CrossRef PubMed ADS Google Scholar

[13] Jović BM, Lačnjevac U, Jović VD, et al. Ni-(Ebonex-supported Ir) composite coatings as electrocatalysts for alkaline water electrolysis. Part II: Oxygen evolution. Int J Hydrogen Energ, 2016, 41: 20502-20514 CrossRef Google Scholar

[14] Li H, Wang Y, Na H, et al. Rechargeable Ni-Li battery integrated aqueous/nonaqueous system. J Am Chem Soc, 2009, 131: 15098-15099 CrossRef PubMed Google Scholar

[15] Stacy J, Regmi YN, Leonard B, et al. The recent progress and future of oxygen reduction reaction catalysis: a review. Renew Sustain Energ Rev, 2017, 69: 401-414 CrossRef Google Scholar

[16] Konopka A, Oliver L, Jr. RFT. The use of carbon substrate utilization patterns in environmental and ecological microbiology. Microbial Ecology, 1998, 35: 103-115 CrossRef Google Scholar

[17] Faunce TA, Lubitz W, Rutherford AWB, et al. Energy and environment policy case for a global project on artificial photosynthesis. Energ Environ Sci, 2013, 6: 695-698 CrossRef Google Scholar

[18] Wang X, Li X, Sun X, et al. Nanostructured NiO electrode for high rate Li-ion batteries. J Mater Chem, 2011, 21: 3571-3573 CrossRef Google Scholar

[19] Lu Q, Lattanzi MW, Chen Y, et al. Supercapacitor electrodes with high-energy and power densities prepared from monolithic NiO/Ni nanocomposites. Angew Chem Int Ed, 2011, 50: 6847-6850 CrossRef PubMed Google Scholar

[20] Dong Y, Liu M, Liu Y, et al. Molybdenum-doped mesoporous carbon/graphene composites as efficient electrocatalysts for the oxygen reduction reaction. J Mater Chem A, 2015, 3: 19969-19973 CrossRef Google Scholar

[21] Yang H, Liu J, Wang J, et al. Electrocatalytically active graphene supported MMo carbides (M=Ni, Co) for oxygen reduction reaction. Electrochim Acta, 2016, 216: 246-252 CrossRef Google Scholar

[22] Zheng Y, Jiao Y, Ge L, et al. Two-step boron and nitrogen doping in graphene for enhanced synergistic catalysis. Angew Chem Int Ed, 2013, 52: 3110-3116 CrossRef PubMed Google Scholar

[23] Song W, Ren Z, Chen SY, et al. Ni- and Mn-promoted mesoporous Co3O4: a stable bifunctional catalyst with surface-structure-dependent activity for oxygen reduction reaction and oxygen evolution reaction. ACS Appl Mater Interfaces, 2016, 8: 20802-20813 CrossRef Google Scholar

[24] Aijaz A, Masa J, Rösler C, et al. Co@Co3O4 encapsulated in carbon nanotube-grafted nitrogen-doped carbon polyhedra as an advanced bifunctional oxygen electrode. Angew Chem Int Ed, 2016, 55: 4087-4091 CrossRef PubMed Google Scholar

[25] Pérez-Alonso FJ, Adán C, Rojas S, et al. Ni/Fe electrodes prepared by electrodeposition method over different substrates for oxygen evolution reaction in alkaline medium. Int J Hydrogen Energ, 2014, 39: 5204-5212 CrossRef Google Scholar

[26] Masa J, Weide P, Peeters D, et al. Amorphous cobalt boride (Co2B) as a highly efficient nonprecious catalyst for electrochemical water splitting: oxygen and hydrogen evolution. Adv Energ Mater, 2016, 6: 1502313 CrossRef Google Scholar

[27] Li X, Dhanabalan A, Bechtold K, et al. Binder-free porous core–shell structured Ni/NiO configuration for application of high performance lithium ion batteries. Electrochem Commun, 2010, 12: 1222-1225 CrossRef Google Scholar

[28] Sun X, Si W, Liu X, et al. Multifunctional Ni/NiO hybrid nanomembranes as anode materials for high-rate Li-ion batteries. Nano Energ, 2014, 9: 168-175 CrossRef Google Scholar

[29] Guo S, Liu W, Meng H, et al. Exchange bias and its training effect in Ni/NiO nanocomposites. J Alloys Compd, 2010, 497: 10-13 CrossRef Google Scholar

[30] Liang Z, Huo R, Yin YX, et al. Carbon-supported Ni@NiO/Al2O3 integrated nanocomposite derived from layered double hydroxide precursor as cycling-stable anode materials for lithium-ion batteries. Electrochim Acta, 2013, 108: 429-434 CrossRef Google Scholar

[31] Arico E, Tabuti F, Fonseca FC, et al. Carbothermal reduction of the YSZ–NiO solid oxide fuel cell anode precursor by carbon-based materials. J Therm Anal Calorim, 2009, 97: 157-161 CrossRef Google Scholar

[32] Lv W, Xiang J, Wen F, et al. Chemical vapor synthesized WS2-embedded polystyrene-derived porous carbon as superior long-term cycling life anode material for li-ion batteries. Electrochim Acta, 2015, 153: 49-54 CrossRef Google Scholar

  • Figure 1

    Schematic illustration of the formation of Ni@NiO@C nanocomposites.

  • Figure 2

    (a) SEM image, (b) low- and (c) high-magnification TEM images, and (d) HRTEM image of the Ni@NiO@C nanocomposites.

  • Figure 3

    (a) XRD pattern, (b) Raman spectrum, (c) nitrogen adsorption-desorption isotherms, and (d) pore size distribution calculated from the adsorption isotherms of Ni@NiO@C nanocomposites.

  • Figure 4

    ORR catalytic activities of Ni@NiO@C. (a) CV curves of Ni@NiO@C in N2-saturated (black dashed line) and O2-saturated (red solid line) 1 mol L−1 KOH at a scan rate of 50 mV s−1. (b) Polarization curves of Ni@NiO@C at various rotation speeds with a scan rate of 5 mV s−1. (c) The corresponding KL plots at various potentials. (d) Current-time chronoamperometric response of Ni@NiO@C in O2-saturated 0.1 mol L−1 KOH at 0.3 V with a rotation speed of 1600 rpm for 15 h.

  • Figure 5

    Electrocatalytic OER performances of Ni@NiO@C nanocomposites: (a) OER polarization curve, (b) calculated Tafel slope, (c) cycling durability test, and (d) the chronoamperometric response measured at a current density of 10 mA cm−2 over 7 h.

  • Figure 6

    Electrochemical performances of the Ni@NiO@C nanocomposites for LIB applications: (a) CV curves, (b) galvanostatic discharge/charge voltage profiles at 200 mA g−1, (c) tests of rate performance at the increased rates from 100 to 1500 mA g−1, and (d) cycling performance at 200 mA g−1.

Copyright 2020 Science China Press Co., Ltd. 《中国科学》杂志社有限责任公司 版权所有