Capacity loss of non-aqueous Li-Air battery due to insoluble product formation: Approximate solution and experimental validation

Yuan, Hao; Read, Jeffrey; Wang, Yun

doi:10.1016/j.mtener.2019.100360

Cited by 6 publications

(6 citation statements)

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“…In most cases, their mixtures of various composition ratios are employed to enhance the performance of electrolytes. 19,20,[22][23][24] Even though intense reactions between Li and water can be prevented by using nonaqueous electrolytes, lightmetal-based batteries may be damaged, burned, or exploded, 19,20 e.g. electric vehicle fires by damaging lithium-ion batteries in case of car accidents.…”

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confidence: 99%

Experimental Measurement of Molecular Diffusion and Evaporation Rate of Battery Organic Electrolytes in Ambient Air

Seo

Wang

2021

J. Electrochem. Soc.

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In this paper, we measured the molecular diffusivity and evaporation rate of organic solvents—1,2-dimethoxyethane (DME), dimethyl carbonate (DMC), diethyl carbonate (DEC), and propylene carbonate (PC)—in ambient air, which are commonly used in light metal batteries, such as Li-ion, Li-air, and Na-O2 batteries. The measurement was conducted through the evolution of the evaporation rate of a liquid solvent in a glass tube, which was designed based on a one-dimensional (1-D) mass transfer model. The experiment successfully measured the diffusion coefficients of DME (0.0925 cm2 s−1), DMC (0.2116 cm2 s−1), and DEC (0.0569 cm2 s−1) in dry air, but failed for that of PC. The PC testing showed a liquid loss smaller than the measurement uncertainty due to its slow evaporation rate under the experimental condition. In the ambient air with the relative humidity (RH) of 50 ± 5%, higher water-soluble solvents showed more decrease in diffusivity calculation compared to that under the dry condition, which is likely due to uncertainty arising from water dissolving to the testing liquid. In addition, we also investigated the time constant for experimental measurement. For the organic liquids, the effective running time can be up to 10 days under room temperature.

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Experimental Measurement of Molecular Diffusion and Evaporation Rate of Battery Organic Electrolytes in Ambient Air

Seo

Wang

2021

J. Electrochem. Soc.

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“…From the perspective of whole battery operation, the sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) decreased the formation and decomposition of solid lithium peroxide (Li2O2) (2 Li + + O 2 + 2e − ↔ Li 2 O 2 , E 0 = 2.96 V), 19 thus leading to many technical issues, i.e., cathode passivation with irreversible damage to the cathode associated with the capacity loss, accumulation of discharge products and by-products (LiOH and/or Li2CO3, etc.). [20][21][22] To optimize the OER kinetics, various catalysts, including noble metals, [23][24][25][26] transition metal oxides, [27][28][29] nitrides [30][31][32] and perovskites, [33][34] have been used. However, the severe accumulation of degraded Li2O2 at the Li2O2/electrode interface readily interrupts the reaction on the electrode.…”

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confidence: 99%

A Ga–Sn liquid metal-mediated structural cathode for Li–O2 batteries

Luo

Yin

et al. 2020

Materials Today Energy

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One of the recent challenges in Li-O2 battery technology is the cycle life, which can be severely shortened by cathode passivation induced by discharge product accumulation; this can be eliminated by reducing the amount of discharge products. Herein, we report a feasibility study on the development of a Ga-Sn liquid metal (LM) functionalized multi-walled carbon nanotubes (MWNTs) cathode. In a comparison of MWNT, LM, m-LM/MWNT (pre-mixed LM and MWNTs), and LM/MWNT (LM modified MWNTs) cathodes, morphology analysis showed that small Li2O2 flakes rather than large crystals grown on the conductive Ga-Sn LM and MWNTs of the LM/MWNT cathode only. The decomposition of the flaky Li2O2 on the LM/MWNT cathode occurred at lower charge overpotentials, resulting in low polarization; thus, the cathode passivation and the consumption of the Li anode were both alleviated during the cyclic process. The LM/MWNT cathode significantly improved the cycle life, rate performance and ultimate capacity of Li-O2 batteries.

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“…Their findings showed that the cathode is the major component having tremendous impact on the performance of the battery, particularly, on specific discharge capacity. Early attempts 7,[10][11][12][13] to enhance the discharge capacity, exhibited that the attained practical capacity of LAB is lower compared to theoretical one (3862 mAh g −1 ). 14 This limited discharge capacity is mainly due to critical challenges imposed by the deposition of lithium peroxide (Li 2 O 2 , discharge product) inside the porous cathode.…”

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confidence: 96%

“…This choked the pores, resulting in limited oxygen diffusivity through the porous cathode. Wang and coworkers 12 investigated the influence of discharge current densities on the discharge capacity. They found that lower discharge currents resulted in a higher capacity (due to formation of Li 2 O 2 toroid and aggregates).…”

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“…Thus, it is deduced that capacity limitation at lower discharge currents is due to pore clogging and lower oxygen transport, while at higher discharge currents, higher electron resistance and blockage of active surface area are responsible for limited cell capacity. 16,19,20 Several continuum models can be found in the literature 12,13,[21][22][23] for aprotic LAB, mostly devoted to identifying the parameters that influence the discharge capacity of lithium air battery. These studies suggested that the porosity of the air electrode is one of the most important parameters to be optimized in order to enhance the discharge capacity.…”

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Modeling of Hierarchical Cathodes for Li-Air Batteries with Improved Discharge Capacity

Hayat¹,

Vega²,

Alhajaj³

2021

J. Electrochem. Soc.

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The non-aqueous Li-air battery is considered to be a promising energy source for electric-vehicles owing to its ultrahigh theoretical power density. However, its commercialization is limited by the attained lower energy density value, which is mainly due to pore blockage and passivation which requires a more strategic design of the cathode. In this work, we have developed and validated a detailed one-dimensional continuum model of Li-Air battery that helps in examining the potential of hierarchical cathodes in guiding and enhancing the efficiency of ions transport and discharge product formation inside microstructures. The obtained results reveal the importance of reducing the tortuosity (shorten the path of oxygen transport) and increasing porosity at the airside of the hierarchical cathode, which improved discharge capacity at approximately 20.9 and 56%, respectively. The improved capacity is due to enhanced effective oxygen transport, impregnation of electrolyte, alignment of pores, and formation of permeable and low crystalline aggregates of Li2O2. Hence, strategies considering these insights can help in the design and fabrication of non-aqueous Li-air batteries with enhanced power density and capacity.

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Capacity loss of non-aqueous Li-Air battery due to insoluble product formation: Approximate solution and experimental validation

Cited by 6 publications

References 45 publications

Experimental Measurement of Molecular Diffusion and Evaporation Rate of Battery Organic Electrolytes in Ambient Air

Experimental Measurement of Molecular Diffusion and Evaporation Rate of Battery Organic Electrolytes in Ambient Air

A Ga–Sn liquid metal-mediated structural cathode for Li–O2 batteries

Modeling of Hierarchical Cathodes for Li-Air Batteries with Improved Discharge Capacity

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