Understanding Rechargeable Li−O<sub>2</sub> Batteries via First‐Principles Computations

Zhang, Xu; Chen, An; Jiao, Menggai; Xie, Zhaojun; Zhou, Zhen

doi:10.1002/batt.201900010

Cited by 31 publications

(24 citation statements)

References 117 publications

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“…During discharge, the catalytic Li 2 O 2 production takes place on the MoO monolayer (oxidized top layer of Mo 3 P) with a DFT‐derived overpotential of 0.06 V. The Li 2 O 2 units can then transfer (via ionic liquid) to agglomerated Li 2 O 2 particles, also confirmed by SEM image shown in Figure 3a–f, (Section 19, Supporting Information), leaving a clean MoO layer behind for further catalysis of the Li 2 O 2 production. [ 79,80,63 ] Our DFT‐derived and experimental discharge overpotentials on Mo 3 P are smaller than the values calculated on the bulk Li 2 O 2 surface (0.33 V on the thermodynamically stable majority facet (0001) and 0.12 V on kink sites), [ 49 ] confirming the viewpoint that discharge takes place via catalytic MoO monolayer. For the charging process on the other hand, there can be two possible contributions: 1) dissolution of Li 2 O 2 from the MoO monolayer, 2) dissolution of Li 2 O 2 from the surface of the agglomerated Li 2 O 2 particles formed during the discharge.…”

Section: Figuresupporting

confidence: 59%

Kinetically Stable Oxide Overlayers on Mo₃P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

et al. 2020

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OER) or only remain active for one of the reactions (different ORR/OER rates). [1-5] This can result in high overpotentials-excess energy above its thermodynamic value (2.96 V)-required to form and decompose lithium peroxide (Li 2 O 2) at the cathode during discharge (ORR) and charge (OER) processes, respectively. Numerous metal catalysts such as platinum (Pt), gold (Au), and ruthenium (Ru), as well as non-metallic catalysts such as transition-metal oxides, transition-metal dichalcogenides, and carbon-based catalysts, have been employed to resolve this issue, however, no major breakthrough has been reported to date. [4,6-11] Therefore, designing a highly active catalyst that can minimize the energy barriers-excess input energy-to form and decompose Li 2 O 2 nanoparticles at the cathode is a key challenge for the development of this technology. Electrocatalytic properties of transition metal phosphides have received great attention and been subject of theoretical and experimental studies. [12-16] Wang et al. demonstrated a convenient and straightforward approach to the synthesis of a 3D selfsupported Ni 5 P 4-Ni 2 P nanosheet cathode, very stable in acidic medium with an outstanding hydrogen evolution reaction (HER) activity. [17] Some other studies include development of The main drawbacks of today's state-of-the-art lithium-air (Li-air) batteries are their low energy efficiency and limited cycle life due to the lack of earth-abundant cathode catalysts that can drive both oxygen reduction and evolution reactions (ORR and OER) at high rates at thermodynamic potentials. Here, inexpensive trimolybdenum phosphide (Mo 3 P) nanoparticles with an exceptional activity-ORR and OER current densities of 7.21 and 6.85 mA cm −2 at 2.0 and 4.2 V versus Li/Li + , respectively-in an oxygen-saturated non-aqueous electrolyte are reported. The Tafel plots indicate remarkably low charge transfer resistance-Tafel slopes of 35 and 38 mV dec −1 for ORR and OER, respectively-resulting in the lowest ORR overpotential of 4.0 mV and OER overpotential of 5.1 mV reported to date. Using this catalyst, a Li-air battery cell with low discharge and charge overpotentials of 80 and 270 mV, respectively, and high energy efficiency of 90.2% in the first cycle is demonstrated. A long cycle life of 1200 is also achieved for this cell. Density functional theory calculations of ORR and OER on Mo 3 P (110) reveal that an oxide overlayer formed on the surface gives rise to the observed high ORR and OER electrocatalytic activity and small discharge/charge overpotentials. The advancement of lithium-air (Li-air) batteries, proposed as a potential alternative for existing energy storage systems, is mainly hampered by low energy efficiency and limited cycle life. One of the major drawbacks for today's Li-air batteries is that developed catalysts exhibit sluggish activity for both oxygen reduction and evolution reactions (ORR and

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Section: Figuresupporting

confidence: 59%

Kinetically Stable Oxide Overlayers on Mo₃P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

et al. 2020

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“…As for the OER path way (recharge process), the rate limitation step for inverse is the oxidation of Li 2 O 2 . [51,52] From Figure 5c, we find that LiCoO 2 can decrease the ORR overpotential to 0.591 V, which is smaller than that of ORR process with Li 0.6 CoO 2 (0.663 V). The calculated result agrees well with the results showing in Figure 5a,b.…”

Section: Self-boosting Mechanism Of Licoo 2 For Lobsmentioning

confidence: 89%

Probing the Self‐Boosting Catalysis of LiCoO₂ in Li–O₂ Battery with Multiple In Situ/Operando Techniques

Gao

Zhou

Ning

et al. 2020

Adv Funct Materials

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Designing high-activity catalysts and revealing the in-depth structure-property relationship is particularly important for Li-O 2 batteries. Herein, the self-boosting catalysis of LiCoO 2 as an electrocatalyst for Li-O 2 batteries and the investigation of its self-adjustment mechanism using in situ X-ray absorption spectroscopy and other operando characterization techniques is reported. The intercalation/extraction of Li + in LiCoO 2 not only induces the change in Co valence and modulates the electronic/crystal structure but also tunes the surface disorder degree, lattice strain, and local symmetry, which all affect the catalysis activity. In a discharge, highly ordered LiCoO 2 acts as a catalyst to boost oxygen reduction reaction. During charging, the initial extraction of Li + from LiCoO 2 induces Li/oxygen vacancy and Co 4+ , which deforms CoO 6 octahedron as well as lowers the symmetry, and accordingly promotes oxygen evolution reaction. This article offers insights into tuning the activity of catalysts for Li-O 2 batteries with the intercalation/extraction of alkali metal ions in traditional cathodes.

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“…The OER has a multi‐step pathway containing four‐electron transfer [23] . The traditional reaction equations for OER are summarized as follows [Eqs.…”

Section: Reaction Mechanisms Of Oxygen and Hydrogen Electrocatalysismentioning

confidence: 99%

Controlled Synthesis and Structure Engineering of Transition Metal‐based Nanomaterials for Oxygen and Hydrogen Electrocatalysis in Zinc‐Air Battery and Water‐Splitting Devices

Zhang

Yao³

et al. 2021

ChemSusChem

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Electrocatalytic energy conversion plays a crucial role in realizing energy storage and utilization. Clean energy technologies such as water electrolysis, fuel cells, and metal‐air batteries heavily depend on a series of electrochemical redox reactions occurring on the catalysts surface. Therefore, developing efficient electrocatalysts is conducive to remarkably improved performance of these devices. Among numerous studies, transition metal‐based nanomaterials (TMNs) have been considered as promising catalysts by virtue of their abundant reserves, low cost, and well‐designed active sites. This Minireview is focused on the typical clean electrochemical reactions: hydrogen evolution reaction, oxygen evolution reaction, and oxygen reduction reaction. Recent efforts to optimize the external morphology and the internal electronic structure of TMNs are described, and beginning with single‐component TMNs, the active sites are clarified, and strategies for exposing more active sites are discussed. The summary about multi‐component TMNs demonstrates the complementary advantages of integrating functional compositions. A general introduction of single‐atom TMNs is provided to deepen the understanding of the catalytic process at an atomic scale. Finally, current challenges and development trends of TMNs in clean energy devices are summarized.

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Understanding Rechargeable Li−O₂ Batteries via First‐Principles Computations

Cited by 31 publications

References 117 publications

Kinetically Stable Oxide Overlayers on Mo₃P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

Kinetically Stable Oxide Overlayers on Mo₃P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

Probing the Self‐Boosting Catalysis of LiCoO₂ in Li–O₂ Battery with Multiple In Situ/Operando Techniques

Controlled Synthesis and Structure Engineering of Transition Metal‐based Nanomaterials for Oxygen and Hydrogen Electrocatalysis in Zinc‐Air Battery and Water‐Splitting Devices

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Understanding Rechargeable Li−O2 Batteries via First‐Principles Computations

Cited by 31 publications

References 117 publications

Kinetically Stable Oxide Overlayers on Mo3P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

Kinetically Stable Oxide Overlayers on Mo3P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

Probing the Self‐Boosting Catalysis of LiCoO2 in Li–O2 Battery with Multiple In Situ/Operando Techniques

Controlled Synthesis and Structure Engineering of Transition Metal‐based Nanomaterials for Oxygen and Hydrogen Electrocatalysis in Zinc‐Air Battery and Water‐Splitting Devices

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Product

Resources

About

Understanding Rechargeable Li−O₂ Batteries via First‐Principles Computations

Kinetically Stable Oxide Overlayers on Mo₃P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

Kinetically Stable Oxide Overlayers on Mo₃P Nanoparticles Enabling Lithium–Air Batteries with Low Overpotentials and Long Cycle Life

Probing the Self‐Boosting Catalysis of LiCoO₂ in Li–O₂ Battery with Multiple In Situ/Operando Techniques