Co3O4 functionalized porous carbon nanotube oxygen-cathodes to promote Li2O2 surface growth for improved cycling stability of Li–O2 batteries

Zhou, Yin; Lyu, Zhiyang; Wang, Liangjun; Dong, Wenhao; Dai, Wenrui; Cui, Xinhang; Hao, Zhongkai; Lai, Min; Chen, Wei

doi:10.1039/c7ta09932k

Cited by 34 publications

(28 citation statements)

References 48 publications

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“…Variety of LOBs cathode materials have been reported based on noble metals, noble metal oxides (Au, Pt, Ru, Pd, RuO 2 , etc. ), transition metal oxides (MnO 2 , Co 3 O 4 , TiO 2 , NiO, MnCo 2 O 4 , etc. ), and carbonaceous materials (mesoporous carbon, carbon nanotube, graphene, etc.).…”

Section: Introductionmentioning

confidence: 99%

One‐Step Route Synthesized Co₂P/Ru/N‐Doped Carbon Nanotube Hybrids as Bifunctional Electrocatalysts for High‐Performance Li–O₂ Batteries

Wang

Dong

et al. 2019

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The large‐scale commercial application of lithium–oxygen batteries (LOBs) is overwhelmed by the sluggish kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) associated with insoluble and insulated Li2O2. Herein, an elaborate design on a highly catalytic LOBs cathode constructed by N‐doped carbon nanotubes (CNT) with in situ encapsulated Co2P and Ru nanoparticles is reported. The homogeneously dispersed Co2P and Ru catalysts can effectively modulate the formation and decomposition behavior of Li2O2 during discharge/charge processes, ameliorating the electronically insulating property of Li2O2 and constructing a homogenous low‐impedance Li2O2/catalyst interface. Compared with Co/CNT and Ru/CNT electrodes, the Co2P/Ru/CNT electrode delivers much higher oxygen reduction triggering onset potential and higher ORR and OER peak current and integral areas, showing greatly improved ORR/OER kinetics due to the synergistic effects of Co2P and Ru. Li–O2 cells based on the Ru/Co2P/CNT electrode demonstrate improved ORR/OER overpotential of 0.75 V, excellent rate capability of 12 800 mAh g−1 at 1 A g−1, and superior cycle stability for more than 185 cycles under a restricted capacity of 1000 mAh g−1 at 100 mA g−1. This work paves an exciting avenue for the design and construction of bifunctional catalytic cathodes by coupling metal phosphides with other active components in LOBs.

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Section: Introductionmentioning

confidence: 99%

One‐Step Route Synthesized Co₂P/Ru/N‐Doped Carbon Nanotube Hybrids as Bifunctional Electrocatalysts for High‐Performance Li–O₂ Batteries

Wang

Dong

et al. 2019

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“…The semicircle at high frequencies in Nyquist plots is associated with the charge transfer resistance, which is an effective indicator of monitoring electron transfer capability between the solid‐state discharged products and catalysts. It can be noticeably seen that the impedance value increases apparently after discharge for all the three electrodes, which has also been verified by many other groups . It is well known that the insulating discharge products trapped on the electrode surface can largely passivate active sites, thus inevitably deteriorating the electron transfer ability.…”

Section: Resultsmentioning

confidence: 97%

“…[48,49] And after deep recharge process, these characteristic peaks related to Li 2 O 2 completely disappear, implying that the discharge/charge capacity contributions are mainly derived from the highly reversible formation and decomposition of Li 2 O 2 . [23,44,50] It is well known that the insulating discharge products trapped on the electrode surface can largely passivate active sites, thus inevitably deteriorating the electron transfer ability. The Nyquist plots of the fresh and discharged/recharged NiCo 2 S 4 @NiO, NiCo 2 S 4 , and NiO electrodes are depicted in Figure 7b and Figure S12 (Supporting Information), respectively.…”

Section: Analysis Of the Cathode Electrodes After Discharge And Chargementioning

confidence: 99%

Hierarchical NiCo₂S₄@NiO Core–Shell Heterostructures as Catalytic Cathode for Long‐Life Li‐O₂ Batteries

Wang

Dong

et al. 2019

Advanced Energy Materials

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vehicles. In a typical electrochemical reaction, the discharge product of lithium peroxide (Li 2 O 2 ) can reversibly form and decompose on cathode side during oxygen reduction reaction (ORR) and subsequent oxygen evolution reaction (OER) processes, respectively (O 2 + 2Li + + 2e − ↔ Li 2 O 2 ). [1][2][3][4] Nevertheless, several critical barriers embracing unsatisfactory charge/discharge polarization, poor rate capability, and limited cycle life make the fantastic technology far from practical application, which can be mainly attributed to the intrinsic characteristic of discharge products including insulation property and insolubilization in aprotic electrolytes. During ORR process, Li 2 O 2 precipitations clog the eversmooth passageways of reactants and passivate electrode surfaces, deteriorating electrical connection between catalysts and efficient active sites, raising charge transfer impedance. In OER process, the insulating Li 2 O 2 precipitations are knotty to be composed, delivering unsatisfactory dynamic performance and triggering higher overpotential. [5][6][7][8][9][10] It has been well established that the morphology and distribution of Li 2 O 2 determined by different growth pathway during ORR govern the battery chemistry and hence the electrochemical performance. [11][12][13] Recent works demonstrate that large-sized Li 2 O 2 aggregations (large discs, [14,15] toroids, [16][17][18][19] spheres, [20,21] etc.) contribute to large discharge capacity output during ORR but at the cost of huge charge overpotential during OER, because large sized Li 2 O 2 products do not usually well contact with active sites and are not easily decomposed, thus resulting in a larger charging voltage gap and sluggish charging kinetics. On the contrary, the formation of conformal Li 2 O 2 films or small amorphous Li 2 O 2 particles during ORR can offer much smaller charge transfer resistance and thus improve kinetics performance obviously during the following charge process. [22][23][24][25] Unfortunately, under such condition, the exposed active sites of catalyst matrix would be inactivated quickly, hence leading to a lower discharge capacity. To alleviate this contradiction between large ORR capacity and small OER voltage gap, it mainly focuses on oxygen catalytic cathode to construct elaborate hierarchical porous structures and optimize microstructure of highly efficient dual-catalystThe critical challenges of Li-O 2 batteries lie in sluggish oxygen redox kinetics and undesirable parasitic reactions during the oxygen reduction reaction and oxygen evolution reaction processes, inducing large overpotential and inferior cycle stability. Herein, an elaborately designed 3D hierarchical heterostructure comprising NiCo 2 S 4 @NiO core-shell arrays on conductive carbon paper is first reported as a freestanding cathode for Li-O 2 batteries. The unique hierarchical array structures can build up multidimensional channels for oxygen diffusion and electrolyte impregnation. A built-in interfacial potential between NiCo 2 S 4 and NiO c...

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“…To reveal the cycling performance, the NiFeRu-LDH@GF cathode is tested at a current density of 200 mA g −1 , and a fixed specific capacity of 500 mAh g −1 is a commonly used parameter in LOBs (Zhou et al, 2017;Zhang et al, 2018). The overpotential gradually increases for the charging process, and the terminal voltage is higher than 4.4 V after 46 cycles ( Figure 3B).…”

Section: Resultsmentioning

confidence: 99%

NiFeRu Layered Double Hydroxide and Its Derivatives Supported on Graphite Foam as Binder-Free Cathode for Nonaqueous Li-O2 Batteries

et al. 2020

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Li-O2 batteries (LOBs) generally referred as Li-air batteries (LABs) potentially have a high specific capacity among all kinds of metal-ion batteries. However, it suffers severely from sluggish discharge/charge kinetics. A binder-free integrated cathode is fabricated which contains NiFeRu layered double hydroxide (NiFeRu LDH) nanosheets grown on a 3D conductive graphite foam (NiFeRu LDH@GF) in this work. This integrated 3D cathode exhibits a specific capacity of 3,085 mAh g−1 and a cycle life of 46. The electrochemical performances of NiFeRu LDH derived metal oxides (DMO@GF) by calcining NiFeRu LDH@GF at 350°C, 450°C, and 550°C are also been investigated. The 450°C obtained DMO@GF (450-DMO@GF) exhibits the highest catalytic activity for oxygen reduction/evolution reaction. The unique floccule-like and cross-connected structure of the 450-DMO@GF and its low charge transfer resistance are responsible for the outstanding electrochemical performance.

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Co₃O₄ functionalized porous carbon nanotube oxygen-cathodes to promote Li₂O₂ surface growth for improved cycling stability of Li–O₂ batteries

Abstract: Co3O4 surface functionalized porous carbon nanotubes were designed as an efficient cathode catalyst for Li–O2 batteries, with p-CNT to facilitate Li+ and O2 diffusion, and with Co3O4 to achieve a low charge overpotential.

Cited by 34 publications

References 48 publications

One‐Step Route Synthesized Co₂P/Ru/N‐Doped Carbon Nanotube Hybrids as Bifunctional Electrocatalysts for High‐Performance Li–O₂ Batteries

One‐Step Route Synthesized Co₂P/Ru/N‐Doped Carbon Nanotube Hybrids as Bifunctional Electrocatalysts for High‐Performance Li–O₂ Batteries

Hierarchical NiCo₂S₄@NiO Core–Shell Heterostructures as Catalytic Cathode for Long‐Life Li‐O₂ Batteries

NiFeRu Layered Double Hydroxide and Its Derivatives Supported on Graphite Foam as Binder-Free Cathode for Nonaqueous Li-O2 Batteries

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Co3O4 functionalized porous carbon nanotube oxygen-cathodes to promote Li2O2 surface growth for improved cycling stability of Li–O2 batteries

Abstract: Co3O4 surface functionalized porous carbon nanotubes were designed as an efficient cathode catalyst for Li–O2 batteries, with p-CNT to facilitate Li+ and O2 diffusion, and with Co3O4 to achieve a low charge overpotential.

Cited by 34 publications

References 48 publications

One‐Step Route Synthesized Co2P/Ru/N‐Doped Carbon Nanotube Hybrids as Bifunctional Electrocatalysts for High‐Performance Li–O2 Batteries

One‐Step Route Synthesized Co2P/Ru/N‐Doped Carbon Nanotube Hybrids as Bifunctional Electrocatalysts for High‐Performance Li–O2 Batteries

Hierarchical NiCo2S4@NiO Core–Shell Heterostructures as Catalytic Cathode for Long‐Life Li‐O2 Batteries

NiFeRu Layered Double Hydroxide and Its Derivatives Supported on Graphite Foam as Binder-Free Cathode for Nonaqueous Li-O2 Batteries

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Co₃O₄ functionalized porous carbon nanotube oxygen-cathodes to promote Li₂O₂ surface growth for improved cycling stability of Li–O₂ batteries

One‐Step Route Synthesized Co₂P/Ru/N‐Doped Carbon Nanotube Hybrids as Bifunctional Electrocatalysts for High‐Performance Li–O₂ Batteries

One‐Step Route Synthesized Co₂P/Ru/N‐Doped Carbon Nanotube Hybrids as Bifunctional Electrocatalysts for High‐Performance Li–O₂ Batteries

Hierarchical NiCo₂S₄@NiO Core–Shell Heterostructures as Catalytic Cathode for Long‐Life Li‐O₂ Batteries