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Open AccessOpen Access JUSTC Perspective 05 July 2023

The mystery of Li2O2 formation pathways in aprotic Li–O2 batteries

  • Department of Thermal Science and Energy Engineering, University of Science and Technology of China, Hefei 230026, China

Cite this:
https://doi.org/10.52396/JUSTC-2022-0155
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  • Author Bio:

    Zhuojun Zhang is currently a doctoral student in the Department of Thermal Science and Energy Engineering at the University of Science and Technology of China. His research mainly focus on Li-air batteries, especially the coupled transport phenomena, aiming at improving the electrochemical performance

    Peng Tan is currently a Professor in the Department of Thermal Science and Energy Engineering at the University of Science and Technology of China. His research mainly focuses on the design, characterization, and optimization of advanced energy storage systems, aiming at understanding the coupled heat/mass transfer and electrochemical processes for performance improvement

  • Corresponding author: E-mail: pengtan@ustc.edu.cn
  • Received Date: 31 October 2022
  • Accepted Date: 11 January 2023
    • Available Online: 05 July 2023
    Abstract

  • Abstract

    The solid-state discharge product Li2O2 is closely related to the performance of Li–O2 batteries, which exacerbates the concentration polarization and charge transfer resistance, leading to sudden death and poor cyclability. Although previous theories of the Li2O2 formation pathway help to guide battery design, it is still difficult to explain the full observed Li2O2 behaviors, especially for those with unconventional morphologies. Thus, the pathways of Li2O2 formation remain mysterious. Herein, the evolution of the understanding of Li2O2 formation over the past decades is traced, including the variable Li2O2 morphologies, the corresponding reaction pathways, and the reaction interfaces. This perspective proposes that some Li2O2 particles are strongly dependent on the electrode surface as a result of the dynamic coupling of solution and surface pathways and emphasizes a possible mechanism based on previous experimental results and theories. Further methods are expected to be developed to reveal complex Li2O2 formation pathways and spearhead advanced Li–O2 batteries.

    Graphical abstract

    A new possible Li2O2 formation pathway may couple the dynamic contribution of the solution and surface pathways.

    Abstract

    The solid-state discharge product Li2O2 is closely related to the performance of Li–O2 batteries, which exacerbates the concentration polarization and charge transfer resistance, leading to sudden death and poor cyclability. Although previous theories of the Li2O2 formation pathway help to guide battery design, it is still difficult to explain the full observed Li2O2 behaviors, especially for those with unconventional morphologies. Thus, the pathways of Li2O2 formation remain mysterious. Herein, the evolution of the understanding of Li2O2 formation over the past decades is traced, including the variable Li2O2 morphologies, the corresponding reaction pathways, and the reaction interfaces. This perspective proposes that some Li2O2 particles are strongly dependent on the electrode surface as a result of the dynamic coupling of solution and surface pathways and emphasizes a possible mechanism based on previous experimental results and theories. Further methods are expected to be developed to reveal complex Li2O2 formation pathways and spearhead advanced Li–O2 batteries.

    • Public Summary

    • Reviewing the understanding of Li2O2 formation over the past decade, including the variable morphologies, reaction pathways, and reaction interfaces.
    • Revealing the nonadaptability of previous theories to the partly observed Li2O2 morphologies.
    • Proposing a new possible reaction mechanism coupling the dynamic contribution of the solution and surface pathways to reveal the electrode-dependent Li2O2.

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    • References(28)
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    Wu Z, Tian Y, Chen H, et al. Evolving aprotic Li-air batteries. Chemical Society Reviews, 2022, 51 (18): 8045–101. doi: 10.1039/D2CS00003B
    [2]
    Xu J J, Wang Z L, Xu D, et al. Tailoring deposition and morphology of discharge products towards high-rate and long-life lithium-oxygen batteries. Nature Communications, 2013, 4: 2438. doi: 10.1038/ncomms3438
    [3]
    Olivares-Marín M, Sorrentino A, Lee R C, et al. Spatial distributions of discharged products of lithium-oxygen batteries revealed by synchrotron X-ray transmission microscopy. Nano Letters, 2015, 15 (10): 6932–6938. doi: 10.1021/acs.nanolett.5b02862
    [4]
    Yang C, Wong R A, Hong M, et al. Unexpected Li2O2 film growth on carbon nanotube electrodes with CeO2 nanoparticles in Li–O2 batteries. Nano Letters, 2016, 16 (5): 2969–2974. doi: 10.1021/acs.nanolett.5b05006
    [5]
    Zhai D, Wang H H, Yang J, et al. Disproportionation in Li–O2 batteries based on a large surface area carbon cathode. Journal of the American Chemical Society, 2013, 135 (41): 15364–15372. doi: 10.1021/ja403199d
    [6]
    Griffith L D, Sleightholme A E S, Mansfield J F, et al. Correlating Li/O2 cell capacity and product morphology with discharge current. ACS Applied Materials & Interfaces, 2015, 7 (14): 7670–7678. doi: 10.1021/acsami.5b00574
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    Kwabi D G, Tułodziecki M, Pour N, et al. Controlling solution-mediated reaction mechanisms of oxygen reduction using potential and solvent for aprotic lithium-oxygen batteries. Journal of Physical Chemistry Letters, 2016, 7 (7): 1204–1212. doi: 10.1021/acs.jpclett.6b00323
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    Peng Z, Freunberger S A, Hardwick L J, et al. Oxygen reactions in a non-aqueous Li+ electrolyte. Angewandte Chemie International Edition, 2011, 50 (28): 6351–6355. doi: 10.1002/anie.201100879
    [9]
    Radin M D, Rodriguez J F, Tian F, et al. Lithium peroxide surfaces are metallic, while lithium oxide surfaces are not. Journal of the American Chemical Society, 2012, 134 (2): 1093–1103. doi: 10.1021/ja208944x
    [10]
    Tian F, Radin M D, Siegel D J. Enhanced charge transport in amorphous Li2O2. Chemistry of Materials, 2014, 26 (9): 2952–2959. doi: 10.1021/cm5007372
    [11]
    Viswanathan V, Thygesen K S, Hummelshøj J S, et al. Electrical conductivity in Li2O2 and its role in determining capacity limitations in non-aqueous Li–O2 batteries. The Journal of Chemical Physics, 2011, 135 (21): 214704. doi: 10.1063/1.3663385
    [12]
    Johnson L, Li C, Liu Z, et al. The role of LiO2 solubility in O2 reduction in aprotic solvents and its consequences for Li–O2 batteries. Nature Chemistry, 2014, 6 (12): 1091–1099. doi: 10.1038/nchem.2101
    [13]
    Tan P, Wei Z H, Shyy W, et al. A nano-structured RuO2/NiO cathode enables the operation of non-aqueous lithium-air batteries in ambient air. Energy & Environmental Science, 2016, 9 (5): 1783–1793. doi: 10.1039/C6EE00550K
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    Wong R A, Dutta A, Yang C, et al. Structurally tuning Li2O2 by controlling the surface properties of carbon electrodes: Implications for Li–O2 batteries. Chemistry of Materials, 2016, 28 (21): 8006–8015. doi: 10.1021/acs.chemmater.6b03751
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    Li Y, Zhang R, Chen B, et al. Induced construction of large-area amorphous Li2O2 film via elemental co-doping and spatial confinement to achieve high-performance Li–O2 batteries. Energy Storage Materials, 2022, 44: 285–295. doi: 10.1016/j.ensm.2021.10.026
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    Lu J, Cheng L, Lau K C, et al. Effect of the size-selective silver clusters on lithium peroxide morphology in lithium-oxygen batteries. Nature Communications, 2014, 5: 4895. doi: 10.1038/ncomms5895
    [17]
    Chen L, Yang J, Lu Z, et al. A new type of sealed rechargeable lithium-lithium oxide battery based on reversible LiO2/Li2O2 interconversion. Journal of Materials Chemistry A, 2022, 10 (31): 16570–16577. doi: 10.1039/D2TA03314C
    [18]
    Plunkett S T, Kondori A, Chung D Y, et al. A new cathode material for a Li–O2 battery based on lithium superoxide. ACS Energy Letters, 2022, 7 (8): 2619–2626. doi: 10.1021/acsenergylett.2c01191
    [19]
    Zhang P, Zhao Y, Zhang X. Functional and stability orientation synthesis of materials and structures in aprotic Li–O2 batteries. Chemical Society Reviews, 2018, 47 (8): 2921–3004. doi: 10.1039/C8CS00009C
    [20]
    Prehal C, Mondal S, Lovicar L, et al. Exclusive solution discharge in Li–O2 batteries? ACS Energy Letters, 2022, 7 (9): 3112–3119. doi: 10.1021/acsenergylett.2c01711
    [21]
    Tan C, Cao D, Zheng L, et al. True reaction sites on discharge in Li–O2 batteries. Journal of the American Chemical Society, 2022, 144 (2): 807–815. doi: 10.1021/jacs.1c09916
    [22]
    Zhang Z, Xiao X, Yu W, et al. Reacquainting the sudden-death and reaction routes of Li–O2 batteries by ex situ observation of Li2O2 distribution inside a highly ordered air electrode. Nano Letters, 2022, 22: 7527–7534. doi: 10.1021/acs.nanolett.2c02516
    [23]
    Mitchell R R, Gallant B M, Shao-Horn Y, et al. Mechanisms of morphological evolution of Li2O2 particles during electrochemical growth. The Journal of Physical Chemistry Letters, 2013, 4 (7): 1060–1064. doi: 10.1021/jz4003586
    [24]
    Lee D, Park H, Ko Y, et al. Direct observation of redox mediator-assisted solution-phase discharging of Li–O2 battery by liquid-phase transmission electron microscopy. Journal of the American Chemical Society, 2019, 141 (20): 8047–8052. doi: 10.1021/jacs.9b02332
    [25]
    Tomita K, Noguchi H, Uosaki K. Electrochemical growth of very long (~80 μm) crystalline Li2O2 nanowires on single-layer graphene covered gold and their growth mechanism. Journal of the American Chemical Society, 2020, 142 (46): 19502–19509. doi: 10.1021/jacs.0c05392
    [26]
    Ma S, Yao H, Li Z, et al. Tuning the nucleation and decomposition of Li2O2 by fluorine-doped carbon vesicles towards high performance Li–O2 batteries. Journal of Energy Chemistry, 2022, 70: 614–622. doi: 10.1016/j.jechem.2022.03.007
    [27]
    Wang Y, Lu Y C. Isotopic labeling reveals active reaction interfaces for electrochemical oxidation of lithium peroxide. Angewandte Chemie International Edition, 2019, 58 (21): 6962–6966. doi: 10.1002/anie.201901350
    [28]
    Mo Y, Ong S P, Ceder G. First-principles study of the oxygen evolution reaction of lithium peroxide in the lithium-air battery. Physical Review B, 2011, 84 (20): 205446. doi: 10.1103/PhysRevB.84.205446
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    Figure  1.  Typical morphologies of Li2O2: (a) disc; (b) sheet; (c) toroid; (d) film. (b) Reprinted with permission from Ref. [2]. Copyright 2013, Springer Nature Limited. (c) Reprinted with permission from Ref. [3]. Copyright 2015, American Chemical Society. (d) Reprinted with permission from Ref. [4]. Copyright 2016, American Chemical Society. (e) The evolution of toroidal Li2O2 morphologies with discharge capacity. Reprinted with permission from Ref. [5]. Copyright 2013, American Chemical Society. (f) The effect of current density on Li2O2 particles. Reprinted with permission from Ref. [6]. Copyright 2015, American Chemical Society.

    Figure  2.  Reaction pathways and growth models of Li2O2. Schematic illustration of (a) the dual pathway (solution and surface pathways) and (b) the single solution pathway controlling Li2O2 formation. (a) Reprinted with permissions from Ref. [12]. Copyright 2014, Springer Nature Limited. (b) Reprinted with permissions from Ref. [20]. Copyright 2022, The Authors. Published by American Chemical Society. (c) Li2O2 formation rate and O2− concentration versus normal distance from the electrode surface via (b): Fast association (high k2, dark blue curve) causes fast Li2O2 formation close to the surface, steep O2− concentration gradients, high near-surface nucleation rates and a large number of small particles. Slow association (low k2, light blue curve) results in few, larger particles up to larger distances. Reprinted with permissions from Ref. [20]. Copyright 2022, The Authors. Published by American Chemical Society. (d) Irregular and surface-dependent particles on the end face and inside the channels of the C-AAO electrode. Reprinted with permission from Ref. [22]. Copyright 2022, American Chemical Society. The growth evolution of Li2O2 is proposed via different reaction pathways: (e) two consecutive stages of a toroidal and (f) its layer-by-layer growth model by the solution pathway; (g) the growth of Li2O2 nanowires (NWs) toward the <0001> direction by the surface pathway. (e) Reprinted with permissions from Ref. [24]. Copyright 2019, American Chemical Society. (f) Reprinted with permissions from Ref. [23]. Copyright 2013, American Chemical Society. (g) Reprinted with permission from Ref. [25]. Copyright 2020, American Chemical Society. (h) The possible growth process of half-toroids via a dynamic coupling mechanism.

    [1]
    Wu Z, Tian Y, Chen H, et al. Evolving aprotic Li-air batteries. Chemical Society Reviews, 2022, 51 (18): 8045–101. doi: 10.1039/D2CS00003B
    [2]
    Xu J J, Wang Z L, Xu D, et al. Tailoring deposition and morphology of discharge products towards high-rate and long-life lithium-oxygen batteries. Nature Communications, 2013, 4: 2438. doi: 10.1038/ncomms3438
    [3]
    Olivares-Marín M, Sorrentino A, Lee R C, et al. Spatial distributions of discharged products of lithium-oxygen batteries revealed by synchrotron X-ray transmission microscopy. Nano Letters, 2015, 15 (10): 6932–6938. doi: 10.1021/acs.nanolett.5b02862
    [4]
    Yang C, Wong R A, Hong M, et al. Unexpected Li2O2 film growth on carbon nanotube electrodes with CeO2 nanoparticles in Li–O2 batteries. Nano Letters, 2016, 16 (5): 2969–2974. doi: 10.1021/acs.nanolett.5b05006
    [5]
    Zhai D, Wang H H, Yang J, et al. Disproportionation in Li–O2 batteries based on a large surface area carbon cathode. Journal of the American Chemical Society, 2013, 135 (41): 15364–15372. doi: 10.1021/ja403199d
    [6]
    Griffith L D, Sleightholme A E S, Mansfield J F, et al. Correlating Li/O2 cell capacity and product morphology with discharge current. ACS Applied Materials & Interfaces, 2015, 7 (14): 7670–7678. doi: 10.1021/acsami.5b00574
    [7]
    Kwabi D G, Tułodziecki M, Pour N, et al. Controlling solution-mediated reaction mechanisms of oxygen reduction using potential and solvent for aprotic lithium-oxygen batteries. Journal of Physical Chemistry Letters, 2016, 7 (7): 1204–1212. doi: 10.1021/acs.jpclett.6b00323
    [8]
    Peng Z, Freunberger S A, Hardwick L J, et al. Oxygen reactions in a non-aqueous Li+ electrolyte. Angewandte Chemie International Edition, 2011, 50 (28): 6351–6355. doi: 10.1002/anie.201100879
    [9]
    Radin M D, Rodriguez J F, Tian F, et al. Lithium peroxide surfaces are metallic, while lithium oxide surfaces are not. Journal of the American Chemical Society, 2012, 134 (2): 1093–1103. doi: 10.1021/ja208944x
    [10]
    Tian F, Radin M D, Siegel D J. Enhanced charge transport in amorphous Li2O2. Chemistry of Materials, 2014, 26 (9): 2952–2959. doi: 10.1021/cm5007372
    [11]
    Viswanathan V, Thygesen K S, Hummelshøj J S, et al. Electrical conductivity in Li2O2 and its role in determining capacity limitations in non-aqueous Li–O2 batteries. The Journal of Chemical Physics, 2011, 135 (21): 214704. doi: 10.1063/1.3663385
    [12]
    Johnson L, Li C, Liu Z, et al. The role of LiO2 solubility in O2 reduction in aprotic solvents and its consequences for Li–O2 batteries. Nature Chemistry, 2014, 6 (12): 1091–1099. doi: 10.1038/nchem.2101
    [13]
    Tan P, Wei Z H, Shyy W, et al. A nano-structured RuO2/NiO cathode enables the operation of non-aqueous lithium-air batteries in ambient air. Energy & Environmental Science, 2016, 9 (5): 1783–1793. doi: 10.1039/C6EE00550K
    [14]
    Wong R A, Dutta A, Yang C, et al. Structurally tuning Li2O2 by controlling the surface properties of carbon electrodes: Implications for Li–O2 batteries. Chemistry of Materials, 2016, 28 (21): 8006–8015. doi: 10.1021/acs.chemmater.6b03751
    [15]
    Li Y, Zhang R, Chen B, et al. Induced construction of large-area amorphous Li2O2 film via elemental co-doping and spatial confinement to achieve high-performance Li–O2 batteries. Energy Storage Materials, 2022, 44: 285–295. doi: 10.1016/j.ensm.2021.10.026
    [16]
    Lu J, Cheng L, Lau K C, et al. Effect of the size-selective silver clusters on lithium peroxide morphology in lithium-oxygen batteries. Nature Communications, 2014, 5: 4895. doi: 10.1038/ncomms5895
    [17]
    Chen L, Yang J, Lu Z, et al. A new type of sealed rechargeable lithium-lithium oxide battery based on reversible LiO2/Li2O2 interconversion. Journal of Materials Chemistry A, 2022, 10 (31): 16570–16577. doi: 10.1039/D2TA03314C
    [18]
    Plunkett S T, Kondori A, Chung D Y, et al. A new cathode material for a Li–O2 battery based on lithium superoxide. ACS Energy Letters, 2022, 7 (8): 2619–2626. doi: 10.1021/acsenergylett.2c01191
    [19]
    Zhang P, Zhao Y, Zhang X. Functional and stability orientation synthesis of materials and structures in aprotic Li–O2 batteries. Chemical Society Reviews, 2018, 47 (8): 2921–3004. doi: 10.1039/C8CS00009C
    [20]
    Prehal C, Mondal S, Lovicar L, et al. Exclusive solution discharge in Li–O2 batteries? ACS Energy Letters, 2022, 7 (9): 3112–3119. doi: 10.1021/acsenergylett.2c01711
    [21]
    Tan C, Cao D, Zheng L, et al. True reaction sites on discharge in Li–O2 batteries. Journal of the American Chemical Society, 2022, 144 (2): 807–815. doi: 10.1021/jacs.1c09916
    [22]
    Zhang Z, Xiao X, Yu W, et al. Reacquainting the sudden-death and reaction routes of Li–O2 batteries by ex situ observation of Li2O2 distribution inside a highly ordered air electrode. Nano Letters, 2022, 22: 7527–7534. doi: 10.1021/acs.nanolett.2c02516
    [23]
    Mitchell R R, Gallant B M, Shao-Horn Y, et al. Mechanisms of morphological evolution of Li2O2 particles during electrochemical growth. The Journal of Physical Chemistry Letters, 2013, 4 (7): 1060–1064. doi: 10.1021/jz4003586
    [24]
    Lee D, Park H, Ko Y, et al. Direct observation of redox mediator-assisted solution-phase discharging of Li–O2 battery by liquid-phase transmission electron microscopy. Journal of the American Chemical Society, 2019, 141 (20): 8047–8052. doi: 10.1021/jacs.9b02332
    [25]
    Tomita K, Noguchi H, Uosaki K. Electrochemical growth of very long (~80 μm) crystalline Li2O2 nanowires on single-layer graphene covered gold and their growth mechanism. Journal of the American Chemical Society, 2020, 142 (46): 19502–19509. doi: 10.1021/jacs.0c05392
    [26]
    Ma S, Yao H, Li Z, et al. Tuning the nucleation and decomposition of Li2O2 by fluorine-doped carbon vesicles towards high performance Li–O2 batteries. Journal of Energy Chemistry, 2022, 70: 614–622. doi: 10.1016/j.jechem.2022.03.007
    [27]
    Wang Y, Lu Y C. Isotopic labeling reveals active reaction interfaces for electrochemical oxidation of lithium peroxide. Angewandte Chemie International Edition, 2019, 58 (21): 6962–6966. doi: 10.1002/anie.201901350
    [28]
    Mo Y, Ong S P, Ceder G. First-principles study of the oxygen evolution reaction of lithium peroxide in the lithium-air battery. Physical Review B, 2011, 84 (20): 205446. doi: 10.1103/PhysRevB.84.205446
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