ISSN 0253-2778

CN 34-1054/N

Open AccessOpen Access JUSTC Engineering and Materials Science

Development of the Ag nanoparticle-decorated Co3O4 electrode for high-performance hybrid Zn batteries

Cite this:
https://doi.org/10.52396/JUST-2021-0049
  • Received Date: 11 February 2021
  • Rev Recd Date: 05 May 2021
  • Publish Date: 30 April 2021
  • The hybrid Zn battery is a promising electrochemical system integrating the redox reactions of transition metal oxides and oxygen in a single cell, through which high energy efficiency and energy density can be achieved simultaneously. However, the positive electrode usually suffers from unsatisfactory capacity utilization of the active material and poor oxygen reduction and evolution reaction activity. Here, a novel nano-structured Co3O4 electrode with the decoration of Ag nanoparticles is developed. Benefiting from the synergistic function between Ag nanoparticles and Co3O4 nanowires, the electric conductivity is improved and the morphology is optimized effectively. With this electrode, a hybrid Zn battery delivers five-step discharge voltage plateaus from 1.85 to 1.75, 1.6, 1.55, and 1.3 V, a high active material utilization ratio of 18%, and a low voltage gap of 0.69 V at 1 mA·cm-2. Moreover, it can operate stably for 500 cycles with a voltage gap increase of only 0.03 V at 10 mA·cm-2. This work brings up a novel electrode for an ultra-high performance hybrid Zn battery with both high active material utilization and outstanding oxygen electrocatalytic activity.
    The hybrid Zn battery is a promising electrochemical system integrating the redox reactions of transition metal oxides and oxygen in a single cell, through which high energy efficiency and energy density can be achieved simultaneously. However, the positive electrode usually suffers from unsatisfactory capacity utilization of the active material and poor oxygen reduction and evolution reaction activity. Here, a novel nano-structured Co3O4 electrode with the decoration of Ag nanoparticles is developed. Benefiting from the synergistic function between Ag nanoparticles and Co3O4 nanowires, the electric conductivity is improved and the morphology is optimized effectively. With this electrode, a hybrid Zn battery delivers five-step discharge voltage plateaus from 1.85 to 1.75, 1.6, 1.55, and 1.3 V, a high active material utilization ratio of 18%, and a low voltage gap of 0.69 V at 1 mA·cm-2. Moreover, it can operate stably for 500 cycles with a voltage gap increase of only 0.03 V at 10 mA·cm-2. This work brings up a novel electrode for an ultra-high performance hybrid Zn battery with both high active material utilization and outstanding oxygen electrocatalytic activity.
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  • [1]
    Parker J F, Chervin C N, Pala I R, et al. Rechargeable nickel-3D zinc batteries: An energy-dense, safer alternative to lithium-ion. Science, 2017, 356(6336): 415-418.
    [2]
    Fu J, Cano Z P, Park M G, et al. Electrically rechargeable zinc-air batteries: Progress, challenges, and perspectives. Advanced Materials, 2017, 29(7): 1604685.
    [3]
    Tan P, Chen B, Xu H R, et al. Flexible Zn- and Li-air batteries: Recent advances, challenges, and future perspectives. Energy and Environmental Science, 2017, 10(10): 2056-2080.
    [4]
    Zhu X F, Hu C G, Amal R, et al. Heteroatom-doped carbon catalysts for zinc-air batteries: Progress, mechanism, and opportunities. Energy & Environmental Science, 2020, 13(12): 4536-4563.
    [5]
    Tan P, Chen B, Xu H R, et al. Synthesis of Fe2O3 nanoparticle-decorated n-doped reduced graphene oxide as an effective catalyst for Zn-air batteries. Journal of the Electrochemical Society, 2019, 166(4): A616-A622.
    [6]
    Fu J, Liang R L, Liu G H, et al. Recent progress in electrically rechargeable zinc-air batteries. Advanced Materials, 2018, 29(7): 1805230.
    [7]
    Wang F, Zhang B, Zhang M Y, et al. A rechargeable zinc-air battery based on zinc peroxide chemistry. Science, 2021, 371(6524): 46-51.
    [8]
    Tan Y Y, Zhang Z Y, Lei Z, et al. Thiourea-zeolitic imidazolate framework-67 assembly derived Co-CoO nanoparticles encapsulated in N, S codoped open carbon shell as bifunctional oxygen electrocatalyst for rechargeable flexible solid Zn-air batteries. Journal of Power Sources, 2020, 473: 228570,
    [9]
    Liu X Z, Tang T, Jiang W J, et al. Fe-doped Co3O4 polycrystalline nanosheets as binder-free bifunctional cathode for robust and efficient zinc-air batteries. Chemical Communications, 2020, 56(40): 5374-5377.
    [10]
    Xie S L, Lin J J, Wang S S, et al. Rational design of hybrid Fe7S8/Fe2N nanoparticles as effective and durable bifunctional electrocatalysts for rechargeable zinc-air batteries. Journal of Power Sources, 2020, 457: 228038.
    [11]
    Guo Y B, Yao S, Gao L X, et al. Boosting bifunctional electrocatalytic activity in S and N co-doped carbon nanosheets for high-efficiency Zn-air batteries. Journal of Materials Chemistry A, 2020, 8(8): 4386-4395.
    [12]
    Li S M, Yang X H, Yang S Y, et al. An amorphous trimetallic (Ni-Co-Fe) hydroxide-sheathed 3D bifunctional electrode for superior oxygen evolution and high-performance cable-type flexible zinc-air batteries. Journal of Materials Chemistry A, 2020, 8(11): 5601-5611.
    [13]
    Tan P, Chen B, Xu H R, et al. In-situ growth of Co3O4 nanowire-assembled clusters on nickel foam for aqueous rechargeable Zn-Co3O4 and Zn-air batteries. Applied Catalysis B: Environmental, 2019, 241: 104-112.
    [14]
    Zhong Y T, Xu X M, Liu P Y, et al. A function-separated design of electrode for realizing high-performance hybrid zinc battery. Advanced Energy Materials, 2020, 10: 2002992.
    [15]
    Shang W X, Yu W T, Tan P, et al. Achieving high energy density and efficiency through integration: Progress in hybrid zinc batteries. Journal of Materials Chemistry A, 2019, 7(26): 15564-15574.
    [16]
    Tan P, Chen B, Xu H R, et al. Growth of Al and Co co-doped NiO nanosheets on carbon cloth as the air electrode for Zn-air batteries with high cycling stability. Electrochimica Acta, 2018, 290: 21-29,
    [17]
    Ma Y Y, Xiao X, Yu W T, et al. Mathematical modeling and numerical analysis of the discharge process of an alkaline zinc-cobalt battery. Journal of Energy Storage, 2020, 30: 101432,
    [18]
    He D, Song X Y, Li W Q, et al. Active electron density modulation of Co3O4 based catalysts endows highly oxygen evolution capability. Angewandte Chemie., International Edition, 2020, 59(17): 2-9,
    [19]
    Lu Y Z, Wang J, Zeng S Q, et al. An ultrathin defect-rich Co3O4 nanosheet cathode for high-energy and durable aqueous zinc ion batteries. Journal of Materials Chemistry A, 2019, 7(38): 21678.
    [20]
    Xiao X, Hu X Y, Liang Y, et al. Anchoring NiCo2O4 nanowhiskers in biomass-derived porous carbon as superior oxygen electrocatalyst for rechargeable Zn-air battery. Journal of Power Sources, 2020, 476: 228684.
    [21]
    Tan P, Chen B, Xu H R, et al.Co3O4 nanosheets as active material for hybrid Zn batteries. Small, 2018, 14(21): 1800225.
    [22]
    Liu N, Hu H L, Xu X X, et al. Hybrid battery integrated by Zn-air and Zn-Co3O4 batteries at cell level. Journal of Energy Chemistry, 2020, 49(10): 375-383.
    [23]
    Shang W X, Yu W T, Xiao X, et al. Microstructure-tuned cobalt oxide electrodes for high-performance Zn-Co batteries. Electrochimica Acta, 2020, 353: 136535.
    [24]
    Shang W X, Yu W T, Xiao X, et al. Unravel the influences of Ni substitution on Co-based electrodes for rechargeable alkaline Zn-Co batteries. Journal of Power Sources, 2021, 483: 229192.
    [25]
    Tan P, Wu Z, Chen B, et al. Exploring oxygen electrocatalytic activity and pseudocapacitive behavior of Co3O4 nanoplates in alkaline solutions. Electrochimica Acta, 2019, 310: 86-95.
    [26]
    Tan P, Chen B, Xu H R, et al. Integration of Zn-Ag and Zn-air Batteries: A hybrid battery with the advantages of both. ACS Applied Materials and Interfaces, 2018, 10(43): 36873-36881.
    [27]
    Yuksel R, Alpugan E, Unalan H E. Coaxial silver nanowire/polypyrrole nanocomposite supercapacitors. Organic Electronics, 2018, 52: 272-280.
    [28]
    Huang P S, Qin F, Lee J K. Role of the interface between Ag and ZnO in the electric conductivity of Ag nanoparticle-embedded ZnO. ACS Applied Materials and Interfaces, 2020, 12(4): 4715-4721.
    [29]
    Mao Y Y, Xie J Y, Liu H, et al. Hierarchical core-shell Ag@Ni(OH)2@PPy nanowire electrode for ultrahigh energy density asymmetric supercapacitor. Chemical Engineering Journal, 2020, 405: 126984.
    [30]
    Tan P, Chen B, Xu H R, et al. Nanoporous NiO/Ni(OH)2 Plates Incorporated with carbon nanotubes as active materials of rechargeable hybrid zinc batteries for improved energy efficiency and high-rate capability. Journal of The Electrochemical Society, 2018, 165(10): A2119-A2126.
    [31]
    Tan P, Chen B, Xu H R, et al. Investigation on the electrode design of hybrid Zn-Co3O4/air batteries for performance improvements. Electrochimica Acta, 2018, 283: 1028-1036.
    [32]
    Xu D D, Wu S T, Xu X X, et al. Hybrid Zn battery with coordination-polymer-derived, oxygen-vacancy-rich Co3O4 as a cathode material. ACS Sustainable Chemistry & Engineering, 2020, 8(11): 4384-4391.
    [33]
    Wang X X, Xu X X, Chen J, et al. Combination of Zn-NiCo2S4 and Zn-air batteries at the cell level: A hybrid battery makes the best of both worlds. ACS Sustainable Chemistry and Engineering, 2019, 7(14): 12331-12339.
    [34]
    Qaseem A, Chen F Y, Qiu C Z, et al. Reduced graphene oxide decorated with manganese cobalt oxide as multifunctional material for mechanically rechargeable and hybrid zinc-air batteries. Particle and Particle Systems Characterization, 2017, 34(10): 1-14.
    [35]
    Lee D U, Fu J, Park M G, et al. Self-assembled NiO/Ni(OH)2 nanoflakes as active material for high-power and high-energy hybrid rechargeable battery. Nano Letters, 2016, 16(3): 1794-1802.
    [36]
    Lee K C, Lin S J, Lin C H, et al. Size effect of Ag nanoparticles on surface plasmon resonance. Surface and Coatings Technology, 2008, 202(22-23): 5339-5342.
    [37]
    He B, Tan J J, Liew K Y, et al. Synthesis of size controlled Ag nanoparticles. Journal of Molecular Catalysis A: Chemical, 2004, 221(1-2): 121-126.
    [38]
    Agnihotri S, Mukherji S, Mukherji S. Size-controlled silver nanoparticles synthesized over the range 5-100 nm using the same protocol and their antibacterial efficacy. RSC Advances, 2014, 4(8): 3974-3983.
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    [1]
    Parker J F, Chervin C N, Pala I R, et al. Rechargeable nickel-3D zinc batteries: An energy-dense, safer alternative to lithium-ion. Science, 2017, 356(6336): 415-418.
    [2]
    Fu J, Cano Z P, Park M G, et al. Electrically rechargeable zinc-air batteries: Progress, challenges, and perspectives. Advanced Materials, 2017, 29(7): 1604685.
    [3]
    Tan P, Chen B, Xu H R, et al. Flexible Zn- and Li-air batteries: Recent advances, challenges, and future perspectives. Energy and Environmental Science, 2017, 10(10): 2056-2080.
    [4]
    Zhu X F, Hu C G, Amal R, et al. Heteroatom-doped carbon catalysts for zinc-air batteries: Progress, mechanism, and opportunities. Energy & Environmental Science, 2020, 13(12): 4536-4563.
    [5]
    Tan P, Chen B, Xu H R, et al. Synthesis of Fe2O3 nanoparticle-decorated n-doped reduced graphene oxide as an effective catalyst for Zn-air batteries. Journal of the Electrochemical Society, 2019, 166(4): A616-A622.
    [6]
    Fu J, Liang R L, Liu G H, et al. Recent progress in electrically rechargeable zinc-air batteries. Advanced Materials, 2018, 29(7): 1805230.
    [7]
    Wang F, Zhang B, Zhang M Y, et al. A rechargeable zinc-air battery based on zinc peroxide chemistry. Science, 2021, 371(6524): 46-51.
    [8]
    Tan Y Y, Zhang Z Y, Lei Z, et al. Thiourea-zeolitic imidazolate framework-67 assembly derived Co-CoO nanoparticles encapsulated in N, S codoped open carbon shell as bifunctional oxygen electrocatalyst for rechargeable flexible solid Zn-air batteries. Journal of Power Sources, 2020, 473: 228570,
    [9]
    Liu X Z, Tang T, Jiang W J, et al. Fe-doped Co3O4 polycrystalline nanosheets as binder-free bifunctional cathode for robust and efficient zinc-air batteries. Chemical Communications, 2020, 56(40): 5374-5377.
    [10]
    Xie S L, Lin J J, Wang S S, et al. Rational design of hybrid Fe7S8/Fe2N nanoparticles as effective and durable bifunctional electrocatalysts for rechargeable zinc-air batteries. Journal of Power Sources, 2020, 457: 228038.
    [11]
    Guo Y B, Yao S, Gao L X, et al. Boosting bifunctional electrocatalytic activity in S and N co-doped carbon nanosheets for high-efficiency Zn-air batteries. Journal of Materials Chemistry A, 2020, 8(8): 4386-4395.
    [12]
    Li S M, Yang X H, Yang S Y, et al. An amorphous trimetallic (Ni-Co-Fe) hydroxide-sheathed 3D bifunctional electrode for superior oxygen evolution and high-performance cable-type flexible zinc-air batteries. Journal of Materials Chemistry A, 2020, 8(11): 5601-5611.
    [13]
    Tan P, Chen B, Xu H R, et al. In-situ growth of Co3O4 nanowire-assembled clusters on nickel foam for aqueous rechargeable Zn-Co3O4 and Zn-air batteries. Applied Catalysis B: Environmental, 2019, 241: 104-112.
    [14]
    Zhong Y T, Xu X M, Liu P Y, et al. A function-separated design of electrode for realizing high-performance hybrid zinc battery. Advanced Energy Materials, 2020, 10: 2002992.
    [15]
    Shang W X, Yu W T, Tan P, et al. Achieving high energy density and efficiency through integration: Progress in hybrid zinc batteries. Journal of Materials Chemistry A, 2019, 7(26): 15564-15574.
    [16]
    Tan P, Chen B, Xu H R, et al. Growth of Al and Co co-doped NiO nanosheets on carbon cloth as the air electrode for Zn-air batteries with high cycling stability. Electrochimica Acta, 2018, 290: 21-29,
    [17]
    Ma Y Y, Xiao X, Yu W T, et al. Mathematical modeling and numerical analysis of the discharge process of an alkaline zinc-cobalt battery. Journal of Energy Storage, 2020, 30: 101432,
    [18]
    He D, Song X Y, Li W Q, et al. Active electron density modulation of Co3O4 based catalysts endows highly oxygen evolution capability. Angewandte Chemie., International Edition, 2020, 59(17): 2-9,
    [19]
    Lu Y Z, Wang J, Zeng S Q, et al. An ultrathin defect-rich Co3O4 nanosheet cathode for high-energy and durable aqueous zinc ion batteries. Journal of Materials Chemistry A, 2019, 7(38): 21678.
    [20]
    Xiao X, Hu X Y, Liang Y, et al. Anchoring NiCo2O4 nanowhiskers in biomass-derived porous carbon as superior oxygen electrocatalyst for rechargeable Zn-air battery. Journal of Power Sources, 2020, 476: 228684.
    [21]
    Tan P, Chen B, Xu H R, et al.Co3O4 nanosheets as active material for hybrid Zn batteries. Small, 2018, 14(21): 1800225.
    [22]
    Liu N, Hu H L, Xu X X, et al. Hybrid battery integrated by Zn-air and Zn-Co3O4 batteries at cell level. Journal of Energy Chemistry, 2020, 49(10): 375-383.
    [23]
    Shang W X, Yu W T, Xiao X, et al. Microstructure-tuned cobalt oxide electrodes for high-performance Zn-Co batteries. Electrochimica Acta, 2020, 353: 136535.
    [24]
    Shang W X, Yu W T, Xiao X, et al. Unravel the influences of Ni substitution on Co-based electrodes for rechargeable alkaline Zn-Co batteries. Journal of Power Sources, 2021, 483: 229192.
    [25]
    Tan P, Wu Z, Chen B, et al. Exploring oxygen electrocatalytic activity and pseudocapacitive behavior of Co3O4 nanoplates in alkaline solutions. Electrochimica Acta, 2019, 310: 86-95.
    [26]
    Tan P, Chen B, Xu H R, et al. Integration of Zn-Ag and Zn-air Batteries: A hybrid battery with the advantages of both. ACS Applied Materials and Interfaces, 2018, 10(43): 36873-36881.
    [27]
    Yuksel R, Alpugan E, Unalan H E. Coaxial silver nanowire/polypyrrole nanocomposite supercapacitors. Organic Electronics, 2018, 52: 272-280.
    [28]
    Huang P S, Qin F, Lee J K. Role of the interface between Ag and ZnO in the electric conductivity of Ag nanoparticle-embedded ZnO. ACS Applied Materials and Interfaces, 2020, 12(4): 4715-4721.
    [29]
    Mao Y Y, Xie J Y, Liu H, et al. Hierarchical core-shell Ag@Ni(OH)2@PPy nanowire electrode for ultrahigh energy density asymmetric supercapacitor. Chemical Engineering Journal, 2020, 405: 126984.
    [30]
    Tan P, Chen B, Xu H R, et al. Nanoporous NiO/Ni(OH)2 Plates Incorporated with carbon nanotubes as active materials of rechargeable hybrid zinc batteries for improved energy efficiency and high-rate capability. Journal of The Electrochemical Society, 2018, 165(10): A2119-A2126.
    [31]
    Tan P, Chen B, Xu H R, et al. Investigation on the electrode design of hybrid Zn-Co3O4/air batteries for performance improvements. Electrochimica Acta, 2018, 283: 1028-1036.
    [32]
    Xu D D, Wu S T, Xu X X, et al. Hybrid Zn battery with coordination-polymer-derived, oxygen-vacancy-rich Co3O4 as a cathode material. ACS Sustainable Chemistry & Engineering, 2020, 8(11): 4384-4391.
    [33]
    Wang X X, Xu X X, Chen J, et al. Combination of Zn-NiCo2S4 and Zn-air batteries at the cell level: A hybrid battery makes the best of both worlds. ACS Sustainable Chemistry and Engineering, 2019, 7(14): 12331-12339.
    [34]
    Qaseem A, Chen F Y, Qiu C Z, et al. Reduced graphene oxide decorated with manganese cobalt oxide as multifunctional material for mechanically rechargeable and hybrid zinc-air batteries. Particle and Particle Systems Characterization, 2017, 34(10): 1-14.
    [35]
    Lee D U, Fu J, Park M G, et al. Self-assembled NiO/Ni(OH)2 nanoflakes as active material for high-power and high-energy hybrid rechargeable battery. Nano Letters, 2016, 16(3): 1794-1802.
    [36]
    Lee K C, Lin S J, Lin C H, et al. Size effect of Ag nanoparticles on surface plasmon resonance. Surface and Coatings Technology, 2008, 202(22-23): 5339-5342.
    [37]
    He B, Tan J J, Liew K Y, et al. Synthesis of size controlled Ag nanoparticles. Journal of Molecular Catalysis A: Chemical, 2004, 221(1-2): 121-126.
    [38]
    Agnihotri S, Mukherji S, Mukherji S. Size-controlled silver nanoparticles synthesized over the range 5-100 nm using the same protocol and their antibacterial efficacy. RSC Advances, 2014, 4(8): 3974-3983.

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