Influence of carbon pore size on the discharge capacity of Li–O<sub>2</sub>batteries

Ding, Ning; Chien, Sheau Wei; Hor, T. S. Andy; Lum, Regina; Zong, Yun; Liu, Zhaolin

doi:10.1039/c4ta01745e

Cited by 147 publications

(150 citation statements)

References 68 publications

(70 reference statements)

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“…Because discharge products, such as Li 2 O 2 , continuously accumulate on the surface of cathode catalysts during cycling processes, it can clog electrodes and cause electrodes to electrically disconnected. Therefore, porous carbon materials with rationally designed architectures are highly desirable as cathode materials [177], with the capacity of Li-O 2 batteries using carbon cathodes being mainly determined by the surface area, pore volume and pore size available for the deposition of discharge products [177,178]. Hierarchically porous graphene materials consisting of microporous channels and highly connected nanoscale pores were demonstrated to deliver an exceptionally high capacity of 15,000 mAh g −1 in Li-O 2 batteries [20].…”

Section: Defect and Pore Controlled Carbon Nanostructures For Li-airmentioning

confidence: 99%

Carbon-Based Metal-Free Electrocatalysis for Energy Conversion, Energy Storage, and Environmental Protection

Xiao

Zou

et al. 2018

Electrochem. Energ. Rev.

167

103

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Carbon-based metal-free catalysts possess desirable properties such as high earth abundance, low cost, high electrical conductivity, structural tunability, good selectivity, strong stability in acidic/alkaline conditions, and environmental friendliness. Because of these properties, these catalysts have recently received increasing attention in energy and environmental applications. Subsequently, various carbon-based electrocatalysts have been developed to replace noble metal catalysts for low-cost renewable generation and storage of clean energy and environmental protection through metal-free electrocatalysis. This article provides an up-to-date review of this rapidly developing field by critically assessing recent advances in the mechanistic understanding, structure design, and material/device fabrication of metal-free carbon-based electrocatalysts for clean energy conversion/storage and environmental protection, along with discussions on current challenges and perspectives. Graphical AbstractKeywords Metal-free electrocatalysis · Carbon-based catalysts · Energy conversion and storage · Environmental protection

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Section: Defect and Pore Controlled Carbon Nanostructures For Li-airmentioning

confidence: 99%

Carbon-Based Metal-Free Electrocatalysis for Energy Conversion, Energy Storage, and Environmental Protection

Xiao

Zou

et al. 2018

Electrochem. Energ. Rev.

167

103

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“…The overpotential is significantly smaller than that of other carbon-based cathode materials for Li-O 2 batteries. [36][37][38][39] The corresponding initial charge capacity is 10 770 mAh g − 1 at the current density of 200 mA g − 1 . Therefore, the charge capacity is lower than the discharge capacity, indicating that the Li 2 O 2 product was not totally converted back to the Li + and oxygen.…”

Section: Resultsmentioning

confidence: 99%

Ruthenium nanocrystal decorated vertical graphene nanosheets@Ni foam as highly efficient cathode catalysts for lithium-oxygen batteries

Seo

et al. 2016

NPG Asia Mater

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The electrochemical performance of lithium-oxygen (Li-O 2 ) batteries can be markedly improved through designing the architecture of cathode electrodes with sufficient spaces to facilitate the diffusion of oxygen and accommodate the discharge products, and optimizing the cathode catalyst to promote the oxygen reduction reaction and oxygen evolution reaction (OER). Herein, we report the synthesis of ruthenium (Ru) nanocrystal-decorated vertically aligned graphene nanosheets (VGNS) grown on nickel (Ni) foam. As an effective binder-free cathode catalyst for Li-O 2 batteries, the Ru-decorated VGNS@Ni foam can significantly reduce the charge overpotential via the effects on the OER and achieve high specific capacity, leading to an enhanced electrochemical performance. The Ru-decorated VGNS@Ni foam electrode has demonstrated low charge overpotential of~0.45 V and high reversible capacity of 23 864 mAh g − 1 at the current density of 200 mA g − 1 , which can be maintained for 50 cycles under full charge and discharge testing condition in the voltage range of 2.0-4.2 V. Furthermore, Ru nanocrystal decorated VGNS@Ni foam can be cycled for more than 200 cycles with a low overpotential of 0.23 V under the capacity curtained to be 1000 mAh g − 1 at a current density of 200 mA g − 1 . Ru-decorated VGNS@Ni foam electrodes have also achieved excellent high rate and long cyclability performance. This superior electrochemical performance should be ascribed to the unique three-dimensional porous nanoarchitecture of the VGNS@Ni foam electrodes, which provide sufficient pores for the diffusion of oxygen and storage of the discharge product (Li 2 O 2 ), and the effective catalytic effect of Ru nanocrystals on the OER, respectively. Ex situ field emission scanning electron microscopy, X-ray diffraction, Raman and Fourier transform infrared measurements revealed that Ru-decorated VGNS@Ni foam can effectively decompose the discharge product Li 2 O 2 , facilitate the OER and lead to a high round-trip efficiency. Therefore, Ru-decorated VGNS@Ni foam is a promising cathode catalyst for rechargeable Li-O 2 batteries with low charge overpotential, long cycle life and high specific capacity.

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“…It was found that the binder (Kynar) blocked the majority of pores smaller than 30 nm, decreased the surface area and pore volume and decreased the discharge capacity of the battery. The authors also concluded that the discharge capacity of the battery is mainly determined by meso-pores larger than 30 nm.Ding et al 27 investigated the discharge capacity of lithium-oxygen batteries using commercially available carbon materials. There is no clear correlation between the discharge capacity and the surface area or the porosity of the electrode, but the discharge capacity is found to increase with an increasing pore size.…”

mentioning

confidence: 99%

“…Ding et al 27 investigated the discharge capacity of lithium-oxygen batteries using commercially available carbon materials. There is no clear correlation between the discharge capacity and the surface area or the porosity of the electrode, but the discharge capacity is found to increase with an increasing pore size.…”

mentioning

confidence: 99%

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A Modeling Study of the Pore Size Evolution in Lithium-Oxygen Battery Electrodes

2015

J. Electrochem. Soc.

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This study develops a statistics model that investigates the microstructural evolution of porous electrodes and couples the micro structural changes with a computational fluid dynamics model to simulate the discharge performance of an 800-μm-thick electrode at 1 A/m 2 . This study considers the fact that pores that are too small to hold reactants, smaller than a critical pore size, do not contribute to the discharge of the battery. It is found that when the pore size of the electrode increases, the discharge capacity of the electrode first increases due to the improved mass transfer and then decreases due to the decrease of the effective surface area. For instance, when the critical pore size is set as 10 nm, the discharge capacity gradually increases from 86.6 to 214.8 mAh/g carbon when the mean pore size of the electrode increases from 10 to 50 nm, followed by a capacity decrease to 150.8 mAh/g carbon when the mean pore size further increases to 100 nm. This study also finds that alternating the discharge current between 0 (open circuit condition) and the setting current rate can increase the discharge capacity of the lithium-oxygen battery because the oxygen concentration in the electrode increases during the open circuit condition. The increasing energy demands from portable electronic devices and the target of 300 miles driving range of electric vehicles have placed tremendous pressure on current electrical storage systems. Electric storage technologies with very high specific energy are required in order to meet the ever increasing energy demand without significantly increase the weight of the energy storage system. The lithium-oxygen battery is considered as a promising energy storage technology for portable and transportation applications considering its exceptionally high specific energy. Within four types of lithiumoxygen batteries, 1 the battery using organic electrolyte has attracted the most attention.2 Although the active intermediates may react with non-aqueous electrolytes and produce lithium carbonate, lithium hydroxide, and lithium alkyl carbonate, 3-6 the main product is expected to be Li 2 O 2 2 . The overall reaction happens during charge and discharge of a lithium-oxygen battery using organic electrolyte is:The theoretical energy density of the lithium-oxygen battery is calculated to be 11,680 Wh (kg lithium) −1 or 2,790 Wh (kg lithium and oxygen) −1 . 7 The measured specific energy of lithium-oxygen batteries reported in literature, however, is less than 10% of the theoretical specific energy. 8,9 The power, capacity and efficiency of batteries are restricted by the cathode gas diffusion electrode (GDE), which is typically made from carbon material, considering the high energy density of lithium metal and fast reaction rate of lithium electrode. 6,[10][11][12][13][14] In particular, the low solubility and diffusivity of oxygen in nonaqueous electrolytes limit the current density and the capacity of the battery.9,15-19 Meanwhile, pores with different sizes in the electrode have different im...

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Influence of carbon pore size on the discharge capacity of Li–O₂batteries

Abstract: A direct correlation between carbon pore size and cell capacity has been proposed based on the results obtained from a series of intentionally designed and synthesized porous carbons with uniform pore sizes in the range from 20 to 100 nm.

Cited by 147 publications

References 68 publications

Carbon-Based Metal-Free Electrocatalysis for Energy Conversion, Energy Storage, and Environmental Protection

Carbon-Based Metal-Free Electrocatalysis for Energy Conversion, Energy Storage, and Environmental Protection

Ruthenium nanocrystal decorated vertical graphene nanosheets@Ni foam as highly efficient cathode catalysts for lithium-oxygen batteries

A Modeling Study of the Pore Size Evolution in Lithium-Oxygen Battery Electrodes

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Influence of carbon pore size on the discharge capacity of Li–O2batteries

Abstract: A direct correlation between carbon pore size and cell capacity has been proposed based on the results obtained from a series of intentionally designed and synthesized porous carbons with uniform pore sizes in the range from 20 to 100 nm.

Cited by 147 publications

References 68 publications

Carbon-Based Metal-Free Electrocatalysis for Energy Conversion, Energy Storage, and Environmental Protection

Carbon-Based Metal-Free Electrocatalysis for Energy Conversion, Energy Storage, and Environmental Protection

Ruthenium nanocrystal decorated vertical graphene nanosheets@Ni foam as highly efficient cathode catalysts for lithium-oxygen batteries

A Modeling Study of the Pore Size Evolution in Lithium-Oxygen Battery Electrodes

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Influence of carbon pore size on the discharge capacity of Li–O₂batteries