Fabricating Ir/C Nanofiber Networks as Free‐Standing Air Cathodes for Rechargeable Li‐CO<sub>2</sub> Batteries

Wang, Chengyi; Zhang, Qinming; Zhang, Xin; Wang, Xin‐Gai; Xie, Zhaojun; Zhou, Zhen

doi:10.1002/smll.201800641

Cited by 125 publications

(93 citation statements)

References 35 publications

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“…As shown in Figure 4b, even at a higher current density of 400 mA g −1 , 100 cycles were obtained with low overpotential <1.56 V, further corroborating the excellent stability of the Li-CO 2 batteries with Ru-Cu-G cathodes, with more excellent cycling performance with low overpotential reported to date compared with other cathodes. [21,22,25,27] Figure S21 in the Supporting Information also shows the first discharge curves Adv. Energy Mater.…”

Section: Electrochemical Performances Of Li-co 2 Batteries With Ru-cumentioning

confidence: 99%

“…[22,23] Therefore, catalysts play important roles in Li-CO 2 batteries. [24][25][26][27][28][29] As mentioned above, self-decomposition of Li 2 CO 3 induced a series of parasitic reactions, and further influenced the stability of catalysts during the operation of Li-CO 2 batteries. Only by clarifying the changes of catalysts in this process can we design more stable Li-CO 2 batteries.…”

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Exploiting Synergistic Effect by Integrating Ruthenium–Copper Nanoparticles Highly Co‐Dispersed on Graphene as Efficient Air Cathodes for Li–CO₂ Batteries

Zhang

Yang

et al. 2019

Advanced Energy Materials

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is inevitable in Li-CO 2 batteries, [11,12] Li-CO 2 /O 2 batteries, [8,13] and even Li-air batteries. [14] Exception is that the discharge products could be different without the generation of Li 2 CO 3 under specific conditions including protected anodes and effective electrolytes. [15,16] Li 2 CO 3 decomposes to CO 2 when the potential is higher than 3.8 V versus Li/Li + . Notably, O 2 evolution is not detected, as is expected according to the decomposition reaction 2Li 2 CO 3 → 4Li + + 4 e -+ 2CO 2 + O 2 . Instead, superoxide radicals or "nascent oxygen" form during the self-decomposition of Li 2 CO 3 . [12,17] More accurate verification was performed through chemical probes, which qualitatively detected the existence of singlet oxygen ( 1 O 2 ). [18] Parasitic reactions of electrolytes and catalyst degradation were then induced by Li 2 CO 3 oxidation. [12,18] Therefore, efficient air cathodes are expected to change this situation.The introduction of metal nanoparticles could limit side reactions and promote the interaction between Li 2 CO 3 and C. [11,[19][20][21] Beyond this, metal-organic frameworks or surface modified carbon materials also brought unexpected electrochemical performance. [22,23] Therefore, catalysts play important roles in Li-CO 2 batteries. [24][25][26][27][28][29] As mentioned above, self-decomposition of Li 2 CO 3 induced a series of parasitic reactions, and further influenced the stability of catalysts during the operation of Li-CO 2 batteries. Only by clarifying the changes of catalysts in this process can we design more stable Li-CO 2 batteries. In previous reports, mono metal catalysts (Ru, Cu, Au, and Ni) exhibited outstanding activity toward Li-CO 2 batteries and revealed some changes in electrochemical processes. [19][20][21] Nevertheless, there exist shortcomings with mono metal catalysts from materials preparation to electrochemical processes. First, for example, the preparation for monodispersed Ru nanoparticles was often achieved under mild experimental conditions without the generation of stable crystal surfaces, further affecting catalytic activity in Li-CO 2 batteries. [21,30] Second, the incompatibility between the discharge products and mono metal nanomaterials might lead to severe agglomeration and dropping during long cycles. [20,31] In this work, we designed a composite of ruthenium-copper nanoparticles highly co-dispersed on graphene (Ru-Cu-G), and this composite cathode endows Li-CO 2 batteries with low overpotential and excellent cyclability through their synergistic Li-CO 2 batteries are attractive electrical energy storage devices; however, they still suffer from unsatisfactory electrochemical performance, and the kinetics of CO 2 reduction and evolution reactions must be improved significantly. Herein, a composite of ruthenium-copper nanoparticles highly co-dispersed on graphene (Ru-Cu-G) as efficient air cathodes for Li-CO 2 batteries is designed. The Li-CO 2 batteries with Ru-Cu-G cathodes exhibit ultra-low overpotential and can be operated for 100 cycles with ...

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Section: Electrochemical Performances Of Li-co 2 Batteries With Ru-cumentioning

confidence: 99%

mentioning

confidence: 99%

Exploiting Synergistic Effect by Integrating Ruthenium–Copper Nanoparticles Highly Co‐Dispersed on Graphene as Efficient Air Cathodes for Li–CO₂ Batteries

Zhang

Yang

et al. 2019

Advanced Energy Materials

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107

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“…Researchers are currently searching for new catalysts to enhance both discharging and charging reactions in Li-CO 2 batteries, such as carbon materials, transition metals and their compounds. [20,[22][23][24][25][26] Unfortunately, compared to other metal-gas batteries, Li-CO 2 batteries face more severe problems on discharge product accumulation. Because the main discharge product of Li 2 CO 3 is a thermodynamically stable insulator (Δ f G 0 = −1132.1 kJ mol −1 ) with wide bandgap.…”

Section: Introductionmentioning

confidence: 99%

Realizing Interfacial Electronic Interaction within ZnS Quantum Dots/N‐rGO Heterostructures for Efficient Li–CO₂ Batteries

Wang

Xie

You

et al. 2019

Advanced Energy Materials

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With high theoretical energy density, rechargeable metal–gas batteries (e.g., Li–CO2 battery) are considered as one of the most promising energy storage devices. However, their practical applications are hindered by the sluggish reaction kinetics and discharge product accumulation during battery cycling. Currently, the solutions focus on exploration of new catalysts while the thorough understanding of their underlying mechanisms is often ignored. Herein, the interfacial electronic interaction within rationally designed catalysts, ZnS quantum dots/nitrogen‐doped reduced graphene oxide (ZnS QDs/N‐rGO) heterostructures, and their effects on transformation and deposition of discharge products in the Li–CO2 battery are revealed. In this work, the interfacial interaction can both enhance the catalytic activities of ZnS QDs/N‐rGO heterostructures and induce the nucleation of discharge products to form a homogeneous Li2CO3/C film with excellent electronic transmission and high electrochemical activities. When the batteries cycle within a cutoff specific capacity of 1000 mAh g−1 at a current density of 400 mA g−1, the cycling performance of the Li–CO2 battery using a ZnS QDs/N‐rGO cathode is over 3 and 9 times than those coupled with a ZnS nanosheets (NST)/N‐rGO cathode and a N‐rGO cathode, respectively. This work provides comprehensive understandings on designing catalysts for Li–CO2 batteries as well as other rechargeable metal–gas batteries.

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“…e) Cutoff voltages of the different samples under a controlled capacity of 1000 mA h g −1 at 100 mA g −1 . f) Comparison of cycle performance and charge/discharge voltage gap among Li‐CO 2 batteries reported so far …”

Section: Resultsmentioning

confidence: 99%

A Co‐Doped MnO₂ Catalyst for Li‐CO₂ Batteries with Low Overpotential and Ultrahigh Cyclability

Sun

Guo

et al. 2019

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energy density and good cycle stability is believed as a promising strategy to solve this issue. For example, Li-CO 2 batteries which have been developed on the basis of Li-O 2 batteries have recently attracted attention. This battery system not only offers a high energy density for electrochemical energy storage but also alleviates the greenhouse effect by capturing CO 2 . [5] More recently, Li-CO 2 batteries have been attempted as new energy carriers to store renewable energy, in which Li 2 CO 3 is the main discharge product: 4Li + 3CO 2 + 4e − ↔ 2Li 2 CO 3 + C (E 0 = 2.80 V vs Li/Li). [6][7][8] Unfortunately, this incipient prototype battery can only run about ten cycles. The main bottlenecks are related to two aspects. First, the insert decomposition of Li 2 CO 3 discharge product is prone to adhere on the cathode surface, and then remarkably reduces the capacity. [8] Second, the aggregation of Li 2 CO 3 product will block the channels of gas diffusion and reduce the conductivity of electrode, resulting in a very high charge potential (>4.3 V). [6] In this regard, a cathode with a high surface area which could promote the reversibility of the Li 2 CO 3 discharge product is desirable to accelerate the practical applications of Li-CO 2 batteries. [9] Akin to the development of Li-O 2 batteries, there are two approaches to improve the electrochemical properties of the cathodes. On the one hand, the direct optimization of cathode structures has been regarded as a simple method to improve the properties of Li-CO 2 batteries. For instance, Zhou et al. [10,11] successfully examine graphene and carbon nanotubes (CNTs) as the cathodes, in which Li-CO 2 batteries operate for 20 cycles with an overpotential of 1.78 V at 50 mA g −1 under a limitative capacity of 1000 mA h g −1 . Dai et al. [12] design two graphenebased materials with defective structures for Li-CO 2 batteriesholey graphene and B,N-co-doped holey graphene, which show a cycling lifetime of over 200 cycles at 1 A g −1 , but suffer from a large overpotential (about 1.8 V at 1 A g −1 ). Liu et al. [13] first introduce CNTs which decorated with RuO 2 as cathode materials for Li-CO 2 batteries, which can deliver a high specific capacity together with a lower overpotential.On the other hand, the development of new catalysts is another effective method to enhance the electrochemical properties of Li-CO 2 batteries. For example, the cobalt-titanium-layered oxide-RuO 2 composite with a low over-potential of 0.6 V has Li-CO 2 batteries can not only capture CO 2 to solve the greenhouse effect but also serve as next-generation energy storage devices on the merits of economical, environmentally-friendly, and sustainable aspects. However, these batteries are suffering from two main drawbacks: high overpotential and poor cyclability, severely postponing the acceleration of their applications. Herein, a new Co-doped alpha-MnO 2 nanowire catalyst is prepared for rechargeable Li-CO 2 batteries, which exhibits a high capacity (8160 mA h g −1 at a current density of 100 mA g ...

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Fabricating Ir/C Nanofiber Networks as Free‐Standing Air Cathodes for Rechargeable Li‐CO₂ Batteries

Cited by 125 publications

References 35 publications

Exploiting Synergistic Effect by Integrating Ruthenium–Copper Nanoparticles Highly Co‐Dispersed on Graphene as Efficient Air Cathodes for Li–CO₂ Batteries

Exploiting Synergistic Effect by Integrating Ruthenium–Copper Nanoparticles Highly Co‐Dispersed on Graphene as Efficient Air Cathodes for Li–CO₂ Batteries

Realizing Interfacial Electronic Interaction within ZnS Quantum Dots/N‐rGO Heterostructures for Efficient Li–CO₂ Batteries

A Co‐Doped MnO₂ Catalyst for Li‐CO₂ Batteries with Low Overpotential and Ultrahigh Cyclability

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Fabricating Ir/C Nanofiber Networks as Free‐Standing Air Cathodes for Rechargeable Li‐CO2 Batteries

Cited by 125 publications

References 35 publications

Exploiting Synergistic Effect by Integrating Ruthenium–Copper Nanoparticles Highly Co‐Dispersed on Graphene as Efficient Air Cathodes for Li–CO2 Batteries

Exploiting Synergistic Effect by Integrating Ruthenium–Copper Nanoparticles Highly Co‐Dispersed on Graphene as Efficient Air Cathodes for Li–CO2 Batteries

Realizing Interfacial Electronic Interaction within ZnS Quantum Dots/N‐rGO Heterostructures for Efficient Li–CO2 Batteries

A Co‐Doped MnO2 Catalyst for Li‐CO2 Batteries with Low Overpotential and Ultrahigh Cyclability

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Fabricating Ir/C Nanofiber Networks as Free‐Standing Air Cathodes for Rechargeable Li‐CO₂ Batteries

Exploiting Synergistic Effect by Integrating Ruthenium–Copper Nanoparticles Highly Co‐Dispersed on Graphene as Efficient Air Cathodes for Li–CO₂ Batteries

Exploiting Synergistic Effect by Integrating Ruthenium–Copper Nanoparticles Highly Co‐Dispersed on Graphene as Efficient Air Cathodes for Li–CO₂ Batteries

Realizing Interfacial Electronic Interaction within ZnS Quantum Dots/N‐rGO Heterostructures for Efficient Li–CO₂ Batteries

A Co‐Doped MnO₂ Catalyst for Li‐CO₂ Batteries with Low Overpotential and Ultrahigh Cyclability