High-performance Ni-Co-Mn electrocatalyst recovered from spent lithium-ion battery cathode materials for robust oxygen evolution in acid solution

Abstract

Recovering valuable metals from spent lithium-ion batteries (LIBs) for high value-added application is beneficial for global energy cycling and environmental protection. In this work, we obtain the high-performance N-doped Ni-Co-Mn (N-NCM) electrocatalyst from waste LIBs, for robust oxygen evolution application. Lithium-rich solution and NCM oxides are effectively separated from ternary cathode materials by sulfation roasting and low-temperature water leaching approach, in which the recovery efficiency of Li metal reaches nearly 100%. By facile NH₃ treatment, the incorporation of N into NCM significantly increases the ratio of low-valence state Co²⁺ and Mn²⁺, and the formed Mn—N bond benefits the surface catalytic kinetics. Meanwhile, the N doping induces lattice expansion of the NCM, triggering tensile stress to favor the adsorption of the reactant. Thus, the optimized N-NCM electrocatalyst exhibits the superior overpotentials of 256 and 453 mV to achieve the current density of 10 and 100 mA/cm², respectively, with a low Tafel slope of 37.3 mV/dec. This work provides a fresh avenue for recycling spent LIBs in the future to achieve sustainable development.

References

[[1]] Wang Y-q, An N, Wen L, et al.. Recent progress on the recycling technology of Li-ion batteries [J]. Journal of Energy Chemistry, 2021, 55: 391-419.

[[2]] Natarajan S, Anantharaj S, Tayade R J, et al.. Recovered spinel MnCo₂O₄ from spent lithium-ion batteries for enhanced electrocatalytic oxygen evolution in alkaline medium [J]. Dalton Transactions, 2017, 46(41): 14382-14392.

[[3]] Fan E-s, Li L, Wang Z-p, et al.. Sustainable recycling technology for Li-ion batteries and beyond: Challenges and future prospects [J]. Chemical Reviews, 2020, 120(14): 7020-7063.

[[4]] Lv W-g, Wang Z-h, Cao H-b, et al.. A critical review and analysis on the recycling of spent lithium-ion batteries [J]. ACS Sustainable Chemistry & Engineering, 2018, 6(2): 1504-1521.

[[5]] Ordoñez J, Gago E J, Girard A. Processes and technologies for the recycling and recovery of spent lithiumion batteries [J]. Renewable and Sustainable Energy Reviews, 2016, 60: 195-205.

[[6]] Wei Q, Wu Y-y, Li S-j, et al.. Spent lithium ion battery (LIB) recycle from electric vehicles: A minireview [J]. Science of the Total Environment, 2023, 866: 161380.

[[7]] Li Y-k, Lv W-g, Huang H-l, et al.. Recycling of spent lithium-ion batteries in view of green chemistry [J]. Green Chemistry, 2021, 23(17): 6139-6171.

[[8]] Venkatkarthick R, Niu J-j, Srikhaow A, et al.. New insight into the electrocatalysis of Ni-rich trimetallic NCM-based hydroxides for water oxidation [J]. ACS Applied Energy Materials, 2021, 4(7): 6520-6530.

[[9]] Kosasang S, Gatemala H, Ma N, et al.. Trimetallic spinel-type cobalt nickel-doped manganese oxides as bifunctional electrocatalysts for Zn-air batteries [J]. Batteries & Supercaps, 2020, 3(7): 631-637.

[[10]] Hu C-l, Zhang L, Huang Z-q, et al.. Facet-evolution growth of Mn₃O₄@Co_xMn_3−xO₄ electrocatalysts on Ni foam towards efficient oxygen evolution reaction [J]. Journal of Catalysis, 2019, 369: 105-110.

[[11]] Blasco-Ahicart M, Soriano-López J, Carbó J J, et al.. Polyoxometalate electrocatalysts based on earth-abundant metals for efficient water oxidation in acidic media [J]. Nature Chemistry, 2018, 10(1): 24-30.

[[12]] Li A-l, Ooka H, Bonnet N, et al.. Stable potential windows for long-term electrocatalysis by manganese oxides under acidic conditions [J]. Angewandte Chemie, 2019, 131(15): 5108-5112.

[[13]] Wei J-c, Zhao S-c, Ji L-x, et al.. Reuse of Ni-Co-Mn oxides from spent Li-ion batteries to prepare bifunctional air electrodes [J]. Resources, Conservation and Recycling, 2018, 129: 135-142.

[[14]] Hu X, Xu C-l, Li X-w, et al.. Preferential extraction of lithium from spent cathodes and the regeneration of layered oxides for Li/Na-ion batteries [J]. ACS Applied Materials & Interfaces, 2022, 14(21): 24255-24264.

[[15]] Bae H, Kim Y. Technologies of lithium recycling from waste lithium ion batteries: A review [J]. Materials Advances, 2021, 2(10): 3234-3250.

[[16]] Yang Y-x, Yang H-l, Cao H-b, et al.. Direct preparation of efficient catalyst for oxygen evolution reaction and high-purity Li₂CO₃ from spent LiNi_0.5Mn_0.3Co_0.2O₂ batteries [J]. Journal of Cleaner Production, 2019, 236: 117576.

[[17]] Yang C, Zhang J-l, Cao Z-h, et al.. Sustainable and facile process for lithium recovery from spent LiNi_xCo_yMn_zO₂ cathode materials via selective sulfation with ammonium sulfate [J]. ACS Sustainable Chemistry & Engineering, 2020, 8(41): 15732-15739.

[[18]] 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.

[[19]] Wang Y-c, Zhou T, Jiang K, et al.. Reduced mesoporous Co₃O₄ nanowires as efficient water oxidation electrocatalysts and supercapacitor electrodes [J]. Advanced Energy Materials, 2014, 4(16): 1400696.

[[20]] Ke Q-p, Jin Y-x, Ruan F, et al.. Boosting the activity of catalytic oxidation of 5-hydroxymethylfurfural to 2, 5-diformylfuran over nitrogen-doped manganese oxide catalysts [J]. Green Chemistry, 2019, 21(16): 4313-4318.

[[21]] Wang J, Zhong H-h, Yang J, et al.. Tuning the atomic configuration environment of MnN₄ sites by Co cooperation for efficient oxygen reduction [J]. Journal of Energy Chemistry, 2023, 82: 547-559.

[[22]] Gao Q-qiang. A DFT study of the ORR on M-N₃ (M=Mn, Fe, Co, Ni, or Cu) Co-doped graphene with moiety-patched defects [J]. Ionics, 2020, 26(5): 2453-2465.

[[23]] Maiti S, Maiti K, Curnan M T, et al.. Engineering electrocatalyst nanosurfaces to enrich the activity by inducing lattice strain [J]. Energy & Environmental Science, 2021, 14(7): 3717-3756.

[[24]] Mcglynn J C, Cascallana-Matías I, Fraser J P, et al.. Molybdenum ditelluride rendered into an efficient and stable electrocatalyst for the hydrogen evolution reaction by polymorphic control [J]. Energy Technology, 2018, 6(2): 345-350.

[[25]] Li A-l, Kong S, Guo C-x, et al.. Enhancing the stability of cobalt spinel oxide towards sustainable oxygen evolution in acid [J]. Nature Catalysis, 2022, 5(2): 109-118.

[[26]] Cai Z-x, Xu W, Li F-m, et al.. Electropolymerization fabrication of Co phosphate nanoparticles encapsulated in N, P-codoped mesoporous carbon networks as a 3D integrated electrode for full water splitting [J]. ACS Sustainable Chemistry & Engineering, 2017, 5(1): 571-579.

[[27]] Hu F, Zhu S-l, Chen S-m, et al.. Amorphous metallic NiFeP: A conductive bulk material achieving high activity for oxygen evolution reaction in both alkaline and acidic media [J]. Advanced Materials, 2017, 29(32): 1606570.

[[28]] Liu Z-h, Tan H, Liu D-b, et al.. Promotion of overall water splitting activity over a wide pH range by interfacial electrical effects of metallic NiCo-nitrides nanoparticle/NiCo₂O₄ nanoflake/graphite fibers [J]. Advanced Science, 2019, 6(5): 1801829.

[[29]] Anantharaj S, Karthick K, Kundu S. Spinel cobalt titanium binary oxide as an all-non-precious water oxidation electrocatalyst in acid [J]. Inorganic Chemistry, 2019, 58(13): 8570-8576.

[[30]] Mondschein J S, Kumar K, Holder C F, et al.. Intermetallic Ni₂Ta electrocatalyst for the oxygen evolution reaction in highly acidic electrolytes [J]. Inorganic Chemistry, 2018, 57(10): 6010-6015.

[[31]] Zhou C-y, Han X, Zhu F-y, et al.. Facile synthesis of the encapsulation of Co-based multimetallic alloys/oxide nanoparticles nirtogen-doped carbon nanotubes as electrocatalysts for the HER/OER [J]. International Journal of Hydrogen Energy, 2022, 47(65): 27775-27786.

[[32]] Bredar A R C, Chown A L, Burton A R, et al.. Electrochemical impedance spectroscopy of metal oxide electrodes for energy applications [J]. ACS Applied Energy Materials, 2020, 3(1): 66-98.

[[33]] Yu L, Ren Z. Systematic study of the influence of iR compensation on water electrolysis [J]. Materials Today Physics, 2020, 14: 100253.

[[34]] Qi L, Zheng Z-q, Xing C-y, et al.. 1D nanowire heterojunction electrocatalysts of MnCo₂O₄/GDY for efficient overall water splitting [J]. Advanced Functional Materials, 2022, 32(11): 2107179.

[[35]] Zhang W-z, Chen G-y, Du Y-y, et al.. Large-scale synthesis of Fe-doped amorphous cobalt oxide electrocatalysts at room temperature for the oxygen evolution reaction [J]. ACS Applied Energy Materials, 2022, 5(3): 3129-3136.

[[36]] Faraji M, Yousefzadeh S, Nassar M F, et al.. MnCo₂O₄/N-doped graphene quantum dot vigorously coupled to MXene nanosheet: A bifunctional oxygen electrocatalyst outperforms Pt/IrO₂ benchmark electrocatalysts in metal-air batteries [J]. Journal of Alloys and Compounds, 2022, 927: 167115.

[[37]] Zhang Y-c, Han C-d, Gao J, et al.. NiCo-based electrocatalysts for the alkaline oxygen evolution reaction: A review [J]. ACS Catalysis, 2021, 11(20): 12485-12509.

[[38]] Zhang D-d, Shi J-y, Qi Y, et al.. Quasi-amorphous metallic nickel nanopowder as an efficient and durable electrocatalyst for alkaline hydrogen evolution [J]. Advanced Science, 2018, 5(12): 1801216.