Metal-organic frameworks(MOFs)and MOF-derived materials have attracted great attention as alternatives to noble-metal based electrocatalysts owing to their intriguing structure properties,especially for high efficienc...Metal-organic frameworks(MOFs)and MOF-derived materials have attracted great attention as alternatives to noble-metal based electrocatalysts owing to their intriguing structure properties,especially for high efficiency and stable oxygen reduction reaction(ORR).Herein,we employed a one-pot reaction to make a multimetal(Fe,Co,Cu,and Zn)mixed zeolitic imidazolate framework(MM-ZIF)via adopting a simple in situ redox reaction.Further pyrolysis of the target MM-ZIF,a highly porous carbon polyhedron(FC-C@NC)grafted with abundant carbon nanotubes was obtained,in which ultrasmall Co nanoparticles with partial lattice sites substituted by Fe and Cu were embedded.The obtained FC-C@NC possessed large surface area,highly porous structure,widely-spread metal active sites,and conductive carbon frameworks,contributing to outstanding ORR activity and long-term stability.It displayed superior tolerance to methanol crossover and exceeded the commercial Pt/C catalyst and most previously reported non-noble-metal catalysts.Impressively,the as-produced FC-C@NC-based zinc-air battery afforded an open-circuit potential of 1.466 V,a large specific capacity of 659.5 mAh/g,and a high gravimetric energy density of 784.3 Wh/kgZn,significantly outperforming the Pt/C-based cathode.展开更多
An atomically dispersed FeCo-NC material with the 3D flower-like morphology was used as a unique substrate for the controllable deposition of ultrasmall NiFe layered double hydroxide nanodots(termed as NiFe-NDs)to sim...An atomically dispersed FeCo-NC material with the 3D flower-like morphology was used as a unique substrate for the controllable deposition of ultrasmall NiFe layered double hydroxide nanodots(termed as NiFe-NDs)to simultaneously promote the sluggish kinetics of oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).The size-limiting growth of NiFe-NDs(~4.0 nm in diameter)was realized via the confinement of the 3D flower-like mesoporous structure and the rich N/O functionality of FeCo-NC.Benefiting from the distinctive structure with the simultaneously maximum exposure of both OER and ORR active sites,the NiFe-ND/FeCo-NC composite showed an ORR halfwave potential of 0.85 V and an OER potential of 1.66 V in0.1 mol L-1KOH at 10.0 mA cm-2.In-situ Raman analysis suggested the activity of OER was derived from the Ni sites on NiFe-ND/FeCo-NC.Moreover,the NiFe-ND/FeCo-NC-assembled Zn-air battery(ZAB)exhibited a very small discharge-charge voltage gap of 0.87 V at 20 mA cm-2and robust cycling stability.Furthermore,the NiFe-ND/FeCo-NC composite was also applicable for fabricating all-solid-state ZAB to power wearable electronics with superior cycling stability under deformation.Our work could enlighten a new applicable branch of atomically dispersed metal-nitrogen-carbon materials as unique substrates for fabricating multifunctional electrocatalysts.展开更多
Carbon materials featuring hierarchical pores and atomically dispersed metal sites are promising catalysts for energy storage and conversion applications.Herein,we developed a facile strategy to construct functional c...Carbon materials featuring hierarchical pores and atomically dispersed metal sites are promising catalysts for energy storage and conversion applications.Herein,we developed a facile strategy to construct functional carbon materials with a fluffy peony-like structure and dense binary FeCo-Nx active sites(termed as f-FeCo-CNT).By regulating the metal content in precursors,a three-dimensional(3D)interconnected conductive carbon nanotubes network was in-situ formed throughout the atomically dispersed FeCo-NC matrix during pyrolysis.Taking advantage of rich pore hierarchy and co-existence of highly active FeCo-Nx sites and beneficial FeCo alloy nanoparticles,the f-FeCo-CNT material exhibited excellent bifunctional performance towards oxygen reduction reaction/oxygen evolution reactions(ORR/OER)with respect to the atomically dispersed FeCo-NC(SA-f-FeCo-NC)and commercial Pt/C+Ru02 mixture,surpassing the SA-f-FeCo-NC with a 20 mV higher ORR half-wave potential and a 100 mV lower OER overpotential(at 10.0 mA/cm^2).Remarkably,the f-FeCo-CNT-assembled Zn-air battery(ZAB)possessed a maximum specific power of 195.8 mW/cm^2,excellent rate capability,and very good cycling stability at large current density of 20.0 mA/cm^2.This work provides a facile and feasible synthetic strategy of constructing low-cost cathode materials with excellent comprehensive ZAB performance.展开更多
Rechargeable zinc-air batteries(ZABs)have attracted much attention as the next-generation energy conversion and storage devices due to the abundance and environmental friendliness of zinc(Zn)for anode materials,as wel...Rechargeable zinc-air batteries(ZABs)have attracted much attention as the next-generation energy conversion and storage devices due to the abundance and environmental friendliness of zinc(Zn)for anode materials,as well as the safety and low cost of aqueous electrolytes.However,rational design of nonprecious and low-cost integrated air cathode materials with a desirable bifunctional oxygen electrocatalytic performance remains a great challenge for the commercialization of rechargeable ZABs.In previous research studies,various cost-effective carbon-supported electrocatalysts and light-weight carbon-based current collectors for air cathodes have been developed,showing vast potential in the application of carbon-based materials.To improve the bifunctional performance and integration of air cathodes,efforts with respect to the design of morphology,defects,and synergistic effects of carbon-based materials have been made.In this perspective,the general understanding of the air cathode construction and the battery working mechanism is discussed.The recent progress in the design of carbon-based materials for air cathodes in rechargeable ZABs is summarized.Several possible future research directions and the expected development trends are also discussed,aiming to facilitate the commercialization of advanced rechargeable ZABs in our life.展开更多
Rechargeable zinc-air batteries(ZABs)are a promising energy conversion device,which rely critically on electrocatalysts to accelerate their rate-determining reactions such as oxygen reduction(ORR)and oxygen evolution ...Rechargeable zinc-air batteries(ZABs)are a promising energy conversion device,which rely critically on electrocatalysts to accelerate their rate-determining reactions such as oxygen reduction(ORR)and oxygen evolution reactions(OER).Herein,we fabricate a range of bifunctional M-N-C(metal-nitrogen-carbon)catalysts containing M-Nx coordination sites and M/MxC nanoparticles(M=Co,Fe,and Cu)using a new class ofγ-cyclodextrin(CD)based metal-organic framework as the precursor.With the two types of active sites interacting with each other in the catalysts,the obtained Fe@C-FeNC and Co@C-CoNC display superior alkaline ORR activity in terms of low half-wave(E1/2)potential(~0.917 and 0.906 V,respectively),which are higher than Cu@C-CuNC(~0.829 V)and the commercial Pt/C(~0.861 V).As a bifunctional electrocatalyst,the Co@C-CoNC exhibits the best performance,showing a bifunctional ORR/OER overpotential(ΔE)of~0.732 V,which is much lower than that of Fe@C-FeNC(~0.831 V)and Cu@C-CuNC(~1.411 V),as well as most of the robust bifunctional electrocatalysts reported to date.Synchrotron X-ray absorption spectroscopy and density functional theory simulations reveal that the strong electronic correlation between metallic Co nanoparticles and the atomic Co-N4 sites in the Co@C-CoNC catalyst can increase the d-electron density near the Fermi level and thus effectively optimize the adsorption/desorption of intermediates in ORR/OER,resulting in an enhanced bifunctional electrocatalytic performance.The Co@C-CoNC-based rechargeable ZAB exhibited a maximum power density of 162.80 mW cm^(−2) at 270.30 mA cm^(−2),higher than the combination of commercial Pt/C+RuO2(~158.90 mW cm^(−2) at 265.80 mA cm^(−2))catalysts.During the galvanostatic discharge at 10 mA cm^(−2),the ZAB delivered an almost stable discharge voltage of 1.2 V for~140 h,signifying the virtue of excellent bifunctional ORR/OER electrocatalytic activity.展开更多
为了研究炭黑对锌空气电池空气扩散电极电性能的影响,选用不同种类的炭黑作为锌空气电池空气扩散电极的导电剂,采用辊压法制备出空气扩散电极,测试了空气扩散电极的含液率、极化曲线、使用寿命和所得AA型锌空气电池样品的放电容量,还利...为了研究炭黑对锌空气电池空气扩散电极电性能的影响,选用不同种类的炭黑作为锌空气电池空气扩散电极的导电剂,采用辊压法制备出空气扩散电极,测试了空气扩散电极的含液率、极化曲线、使用寿命和所得AA型锌空气电池样品的放电容量,还利用扫描电镜(SEM)对空气扩散电极催化层的表观形貌进行了观察。研究结果表明,Shawinigan Black AB 50炭黑的疏水性最好,所得空气扩散电极的含液率最低、电性能最好、使用寿命最长,所制AA型锌空气电池样品的放电容量可达4.6 Ah。展开更多
The development of efficient and inexpensive graphene-based electrocatalysts is of great significance to promote the commercial application of fuel cell and metal-air batteries. In this paper, a new type of Co and N c...The development of efficient and inexpensive graphene-based electrocatalysts is of great significance to promote the commercial application of fuel cell and metal-air batteries. In this paper, a new type of Co and N co-doped graphene-like nanocarbon(Co/N-GLC) material was prepared by nano-silicon protection and high temperature pyrolysis.The obtained Co/N-GLC catalyst not only has a similar morphology of graphene, but also possesses a high specific surface area(809 m2 g-1) with hierarchical porous structure(micropores/mesopores), and relative high active dopants content.These properties endow it with a good oxygen reduction activity in alkaline media, which can be comparable to commercial Pt/C catalyst. Moreover, the assembled zinc-air batteries using Co/N-GLC catalyst as the air electrode display a better discharge performance and higher stability compared to that of Pt/C electrode. This work demonstrates that the prepared graphene-like carbon catalyst has a good prospect,which can replace noble metal catalyst at the cathode in metalair batteries.展开更多
基金This study was financially supported by the Natural Science Foundation of China(Grant no.51825201 and 51772008)the National Key Research and Development Program of China(Grant no.2017YFA0206701)National Program for Support of Top-notch Young Professionals,and Changjiang Scholar Program.
文摘Metal-organic frameworks(MOFs)and MOF-derived materials have attracted great attention as alternatives to noble-metal based electrocatalysts owing to their intriguing structure properties,especially for high efficiency and stable oxygen reduction reaction(ORR).Herein,we employed a one-pot reaction to make a multimetal(Fe,Co,Cu,and Zn)mixed zeolitic imidazolate framework(MM-ZIF)via adopting a simple in situ redox reaction.Further pyrolysis of the target MM-ZIF,a highly porous carbon polyhedron(FC-C@NC)grafted with abundant carbon nanotubes was obtained,in which ultrasmall Co nanoparticles with partial lattice sites substituted by Fe and Cu were embedded.The obtained FC-C@NC possessed large surface area,highly porous structure,widely-spread metal active sites,and conductive carbon frameworks,contributing to outstanding ORR activity and long-term stability.It displayed superior tolerance to methanol crossover and exceeded the commercial Pt/C catalyst and most previously reported non-noble-metal catalysts.Impressively,the as-produced FC-C@NC-based zinc-air battery afforded an open-circuit potential of 1.466 V,a large specific capacity of 659.5 mAh/g,and a high gravimetric energy density of 784.3 Wh/kgZn,significantly outperforming the Pt/C-based cathode.
基金financially supported by the National Natural Science Foundation of China(21701101)the National Key Research and Development Project,Key Projects of Intergovernmental International Innovation Cooperation(2018YFE0118200 and 2016YFF0204402)+4 种基金the Fundamental Research Funds for the Central Universities(18CX06063A)the Key Research and Development Project of Shandong Province(2019JZZY010506)the Scientific Research Awards Foundation for Outstanding Young Scientists of Shandong Province(ZR2018JL010)the Joint Fund of Outstanding Young Talents of Shandong Province(ZR2017BB018)the Program of Qingdao Scientific and Technological Innovation High-level Talents Project(172-1-1-zhc)。
文摘An atomically dispersed FeCo-NC material with the 3D flower-like morphology was used as a unique substrate for the controllable deposition of ultrasmall NiFe layered double hydroxide nanodots(termed as NiFe-NDs)to simultaneously promote the sluggish kinetics of oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).The size-limiting growth of NiFe-NDs(~4.0 nm in diameter)was realized via the confinement of the 3D flower-like mesoporous structure and the rich N/O functionality of FeCo-NC.Benefiting from the distinctive structure with the simultaneously maximum exposure of both OER and ORR active sites,the NiFe-ND/FeCo-NC composite showed an ORR halfwave potential of 0.85 V and an OER potential of 1.66 V in0.1 mol L-1KOH at 10.0 mA cm-2.In-situ Raman analysis suggested the activity of OER was derived from the Ni sites on NiFe-ND/FeCo-NC.Moreover,the NiFe-ND/FeCo-NC-assembled Zn-air battery(ZAB)exhibited a very small discharge-charge voltage gap of 0.87 V at 20 mA cm-2and robust cycling stability.Furthermore,the NiFe-ND/FeCo-NC composite was also applicable for fabricating all-solid-state ZAB to power wearable electronics with superior cycling stability under deformation.Our work could enlighten a new applicable branch of atomically dispersed metal-nitrogen-carbon materials as unique substrates for fabricating multifunctional electrocatalysts.
基金This work was financially supported by the National Natural Science Foundation of China(No.21701101)the National Key Research and Development Project(Nos.2018YFE0118200,2016YFF0204402)+5 种基金the Fundamental Research Funds for the Central Universities(No.18CX06063A)the Long-Term Subsidy Mechanism from the Ministry of Finance and the Ministry of Education of China,the Shandong Key Research and Development Project(No.2019JZZY010506)the Shandong Scientific Research Awards Foundation for Outstanding Young Scientists(No.ZR2018JL010)the Shandong Joint Fund of Outstanding Young Talents(No.ZR2017BB018)the Scientific Research Foundation of Shandong University of Science and Technology for Recruited Talents(No.2017RCJJ059)the Program for Tsingtao Al-ion Power and Energy-Storage Battery Research Team in the University(No.17-2-1-1-zhc).
文摘Carbon materials featuring hierarchical pores and atomically dispersed metal sites are promising catalysts for energy storage and conversion applications.Herein,we developed a facile strategy to construct functional carbon materials with a fluffy peony-like structure and dense binary FeCo-Nx active sites(termed as f-FeCo-CNT).By regulating the metal content in precursors,a three-dimensional(3D)interconnected conductive carbon nanotubes network was in-situ formed throughout the atomically dispersed FeCo-NC matrix during pyrolysis.Taking advantage of rich pore hierarchy and co-existence of highly active FeCo-Nx sites and beneficial FeCo alloy nanoparticles,the f-FeCo-CNT material exhibited excellent bifunctional performance towards oxygen reduction reaction/oxygen evolution reactions(ORR/OER)with respect to the atomically dispersed FeCo-NC(SA-f-FeCo-NC)and commercial Pt/C+Ru02 mixture,surpassing the SA-f-FeCo-NC with a 20 mV higher ORR half-wave potential and a 100 mV lower OER overpotential(at 10.0 mA/cm^2).Remarkably,the f-FeCo-CNT-assembled Zn-air battery(ZAB)possessed a maximum specific power of 195.8 mW/cm^2,excellent rate capability,and very good cycling stability at large current density of 20.0 mA/cm^2.This work provides a facile and feasible synthetic strategy of constructing low-cost cathode materials with excellent comprehensive ZAB performance.
基金This study was supported by the National Science Foundation for Excellent Young Scholar(51722403)National Natural Science Foundation of China(51771134)+2 种基金Tianjin Natural Science Foundation for Distinguished Young Scholar(18JCJQJC46500)National Natural Science Foundation of China and Guangdong Province(U1601216)the National Youth Talent Support Program.
文摘Rechargeable zinc-air batteries(ZABs)have attracted much attention as the next-generation energy conversion and storage devices due to the abundance and environmental friendliness of zinc(Zn)for anode materials,as well as the safety and low cost of aqueous electrolytes.However,rational design of nonprecious and low-cost integrated air cathode materials with a desirable bifunctional oxygen electrocatalytic performance remains a great challenge for the commercialization of rechargeable ZABs.In previous research studies,various cost-effective carbon-supported electrocatalysts and light-weight carbon-based current collectors for air cathodes have been developed,showing vast potential in the application of carbon-based materials.To improve the bifunctional performance and integration of air cathodes,efforts with respect to the design of morphology,defects,and synergistic effects of carbon-based materials have been made.In this perspective,the general understanding of the air cathode construction and the battery working mechanism is discussed.The recent progress in the design of carbon-based materials for air cathodes in rechargeable ZABs is summarized.Several possible future research directions and the expected development trends are also discussed,aiming to facilitate the commercialization of advanced rechargeable ZABs in our life.
基金supported by the Shenzhen Government’s Plan of Science and Technology(JCYJ20190808121407676 and 20200813142301001)National Natural Science Foundation of China(22178223 and 22262010)+1 种基金Guangxi Science and Technology Fund for Distinguished High-Talent Introduction Program(No.RZ2200002233AC22035091).
文摘Rechargeable zinc-air batteries(ZABs)are a promising energy conversion device,which rely critically on electrocatalysts to accelerate their rate-determining reactions such as oxygen reduction(ORR)and oxygen evolution reactions(OER).Herein,we fabricate a range of bifunctional M-N-C(metal-nitrogen-carbon)catalysts containing M-Nx coordination sites and M/MxC nanoparticles(M=Co,Fe,and Cu)using a new class ofγ-cyclodextrin(CD)based metal-organic framework as the precursor.With the two types of active sites interacting with each other in the catalysts,the obtained Fe@C-FeNC and Co@C-CoNC display superior alkaline ORR activity in terms of low half-wave(E1/2)potential(~0.917 and 0.906 V,respectively),which are higher than Cu@C-CuNC(~0.829 V)and the commercial Pt/C(~0.861 V).As a bifunctional electrocatalyst,the Co@C-CoNC exhibits the best performance,showing a bifunctional ORR/OER overpotential(ΔE)of~0.732 V,which is much lower than that of Fe@C-FeNC(~0.831 V)and Cu@C-CuNC(~1.411 V),as well as most of the robust bifunctional electrocatalysts reported to date.Synchrotron X-ray absorption spectroscopy and density functional theory simulations reveal that the strong electronic correlation between metallic Co nanoparticles and the atomic Co-N4 sites in the Co@C-CoNC catalyst can increase the d-electron density near the Fermi level and thus effectively optimize the adsorption/desorption of intermediates in ORR/OER,resulting in an enhanced bifunctional electrocatalytic performance.The Co@C-CoNC-based rechargeable ZAB exhibited a maximum power density of 162.80 mW cm^(−2) at 270.30 mA cm^(−2),higher than the combination of commercial Pt/C+RuO2(~158.90 mW cm^(−2) at 265.80 mA cm^(−2))catalysts.During the galvanostatic discharge at 10 mA cm^(−2),the ZAB delivered an almost stable discharge voltage of 1.2 V for~140 h,signifying the virtue of excellent bifunctional ORR/OER electrocatalytic activity.
基金广东省重点科技攻关项目(2002 A 1100601)广州市科技重点攻关项目(025 G 3171)
文摘为了研究炭黑对锌空气电池空气扩散电极电性能的影响,选用不同种类的炭黑作为锌空气电池空气扩散电极的导电剂,采用辊压法制备出空气扩散电极,测试了空气扩散电极的含液率、极化曲线、使用寿命和所得AA型锌空气电池样品的放电容量,还利用扫描电镜(SEM)对空气扩散电极催化层的表观形貌进行了观察。研究结果表明,Shawinigan Black AB 50炭黑的疏水性最好,所得空气扩散电极的含液率最低、电性能最好、使用寿命最长,所制AA型锌空气电池样品的放电容量可达4.6 Ah。
基金supported by the National Natural Science Foundation of China (51602113 and 51702111)China Postdoctoral Science Foundation (2016M590692)
文摘The development of efficient and inexpensive graphene-based electrocatalysts is of great significance to promote the commercial application of fuel cell and metal-air batteries. In this paper, a new type of Co and N co-doped graphene-like nanocarbon(Co/N-GLC) material was prepared by nano-silicon protection and high temperature pyrolysis.The obtained Co/N-GLC catalyst not only has a similar morphology of graphene, but also possesses a high specific surface area(809 m2 g-1) with hierarchical porous structure(micropores/mesopores), and relative high active dopants content.These properties endow it with a good oxygen reduction activity in alkaline media, which can be comparable to commercial Pt/C catalyst. Moreover, the assembled zinc-air batteries using Co/N-GLC catalyst as the air electrode display a better discharge performance and higher stability compared to that of Pt/C electrode. This work demonstrates that the prepared graphene-like carbon catalyst has a good prospect,which can replace noble metal catalyst at the cathode in metalair batteries.
