Lithium (Li) metal batteries have attracted much attention owing to its ultra-high energy density.However,as important part of Li metal batteries,Li anodes still face many challenges,mainly including uncontrolled dend...Lithium (Li) metal batteries have attracted much attention owing to its ultra-high energy density.However,as important part of Li metal batteries,Li anodes still face many challenges,mainly including uncontrolled dendritic Li formation,dramatical volume variation and serious pulverization.Herein,manganese dioxide (MnO_(2)) nanosheet modified nitrogen (N),phosphorus (P) co-doping carbon nanofibers(NPC) on carbon cloth (CC)(MnO_(2)@NPC-CC) is successfully fabricated through electrodeposition approach and further treated with Li by the molten-infusion method to prepare Li based Mn@NPC-CC(Li-Mn@NPC-CC) electrode.The synergy of MnO_(2) and NPC obviously increases the reaction rate between MnO_(2)@NPC-CC and Li and guides even Li distribution over infusion process.Additionally,theoretical calculation,simulation and experimental results further indicate that N,P,Mn multi-doping effectively improves the superior lithiophilicity of Li-Mn@NPC-CC,which induces uniform Li deposition/dissolution to suppress dendrite growth over cycles.Moreover,conductive and porous NPC matrix not only effectively improves the stability of Li-Mn@NPC-CC,but also provides abundant spaces to accelerate the transfer of ion/electron and buffer electrode dimension variation during cycling.Hence,Li-Mn@NPC-CC-based symmetric cells exhibit extra-long cycling life (over 2200 h) with small hysteresis of 20 mV.When the LiMn@NPC-CC anode couples with air,Li iron phosphate (LiFePO_(4)),or hard carbon (C) cathode,the assembled full cells exhibit outstanding performance with low hysteresis and stable cycling properties.Especially,the corresponding pouch-typed Li–air cells also exhibit good performance at different bending angles and even power a series of electronic devices.展开更多
Designing the highly catalytic activity and durable bifunctional catalysts toward oxygen reduction/evolution reaction(ORR/OER) is paramount for metal–air batteries. Metal–organic frameworks(MOFs)-based materials hav...Designing the highly catalytic activity and durable bifunctional catalysts toward oxygen reduction/evolution reaction(ORR/OER) is paramount for metal–air batteries. Metal–organic frameworks(MOFs)-based materials have attracted a great deal of attention as the potential candidate for effectively catalyzing ORR/OER due to their adjustable composition and porous structure. Herein, we first introduce the Mn species into zeolitic-imidazole frameworks(ZIFs) and then further pyrolyze the Mn-containing bimetallic ZIFs to synthesize core-shell-structured Co@Co4N nanoparticles embedded into MnO-modified porous N-doped carbon nanocubes(Co@Co4N/MnO–NC). Co@Co4N/MnO–NC exhibits the outstanding catalytic activity toward ORR and OER which is attributed to its abundant pyridinic/graphitic N and Co4N,the optimized content of MnO species, highly dispersed catalytic sites and porous carbon matrix. As a result, the Co@Co4N/MnO–NC-based Zn–air battery exhibits enhanced performances, including the high discharge capacity(762 mA h gZn-1), large power density(200.5 mW cm-2), stable potential profile over 72 h, low overpotential(<1.0 V) and superior cycling life(2800 cycles). Moreover, the belt-shaped Co@Co4N/MnO–NC cathode-based Zn–air batteries are also designed which exhibit the superb electrochemical properties at different bending/twisting conditions.展开更多
Lithium (Li)-CO_(2) battery is rising as an attractive energy-storage system with the competence of CO_(2) conversion/fixation. However, its practical development is seriously hindered by the high overpotential. Herei...Lithium (Li)-CO_(2) battery is rising as an attractive energy-storage system with the competence of CO_(2) conversion/fixation. However, its practical development is seriously hindered by the high overpotential. Herein, a rational design on a highly catalytic Li-CO_(2) battery electrode built by graphdiyne powder as a multi-functional laminar scaffold with anchored highly dispersed Ru nanoparticles is explored. The strong interaction between the abundant acetylenic bond sites of graphdiyne scaffold and Ru nanoparticles can effectively promote the electrochemical progress and reduce the voltage polarization. The unique channels architecture of the cathodic catalyst with enough space not only accelerates CO_(2) diffusion and electrons/Li+ transport, but also allows a large amount of accommodation for discharged product (Li2CO3) to assure an advanced capacity. The corresponding Li-CO_(2) battery displays an advanced discharged capacity of 15,030 mAh/g at 500 mA/g, great capacity retention of 8873 mAh/g at 2 A/g, high coulombic efficiency of 97.6% at 500 mA/g and superior life span for 120 cycles with voltage gap of 1.67 V under a restricted capacity of 1000 mAh/g at 500 mA/g. Ex/in-situ studies prove that synergy between Ru nanoparticles and acetylene bonds of GDY can boost the round-trip CO_(2)RR and CO_(2)ER kinetics.展开更多
Lithium(Li)-O_(2)batteries have triggered worldwide interest due to their ultrahigh theoretical energy density.However,it is a long shot for the grand-scale applications of Li-O_(2)battery at current stage owing to it...Lithium(Li)-O_(2)batteries have triggered worldwide interest due to their ultrahigh theoretical energy density.However,it is a long shot for the grand-scale applications of Li-O_(2)battery at current stage owing to its significant polarization,inferior cycling life,and irreversible decomposition of Li2O_(2).Herein,a facile way of preparing the highly dispersed Co-based nanoparticles encapsulated into porous N-doping carbon polyhedral with the low content of Ru modification(LRu@HDCo-NC)is explored through the pyrolysis of Co/Zn based zeolitic imidazole frameworks(ZIFs)containing Ru-based ligands.Even with the very small amount of Ru introduction(1.8%),LRu@HDCo-NC still exhibits the superior oxygen evolution reaction/oxygen reduction reaction(OER/ORR)performance and also inhibits side reactions in Li-O_(2)battery because of the abundant pores,plentiful surface N heteroatoms,and highly dispersed metal-based sites which are induced by the volatilization of Zn,and conductive/stable carbon skeleton derived from ZIFs.When applied in Li-O_(2)batteries,LRu@HDCo-NC cathode delivers a high discharge capacity of 15,973 mAh·g^(-1)at 200 mA·g^(-1),good capacity retention at higher rate(12,362 mAh·g^(-1)at 500 mA·g^(-1))and outstanding stability for>300 cycles with low voltage polarization of<2.3 V under a cut-off capacity of 1,000 mAh·g^(-1)at 500 mA·g^(-1).More critically,a series of ex situ and in situ characterization technologies disclose that the LRu@HDCo-NC cathodes can effectively promote the reversible reactions in Li-O_(2)batteries.展开更多
清洁能源支撑的电解海水技术是公认的最有前途的未来可持续绿色制氢途径.商用贵金属催化剂储量低、成本昂贵,且在复杂离子环境下容易快速失活的特性,严重阻碍了电解海水技术的工业化发展.本工作通过Ni掺杂Fe团簇催化碳纳米管生长,再气...清洁能源支撑的电解海水技术是公认的最有前途的未来可持续绿色制氢途径.商用贵金属催化剂储量低、成本昂贵,且在复杂离子环境下容易快速失活的特性,严重阻碍了电解海水技术的工业化发展.本工作通过Ni掺杂Fe团簇催化碳纳米管生长,再气体磷化法,成功构建了一种含Ni掺杂FeP纳米颗粒封端的新型氮掺杂碳纳米管交织结构(NFP@NC).独特的N-CNTs交织网络,以及N-CNTs和Ni掺杂FeP的强相互作用提供了快速的传质途径,提高了气体逸出效率,并显著增强了催化剂稳定性.NFP@NC在10 mA cm^(−2)的电流密度下的析氧反应过电位为280 mV,析氢反应过电位为206 mV,低于大多数报道的铁基催化剂.本研究为构建交织的碳纳米管网络和制备高性能双功能海水电解催化剂提供了一种有效的途径.展开更多
基金funding support from the National Natural Science Foundation of China (21905151 and 51772162)the Youth Innovation and Technology Foundation of Shandong Higher Education Institutions, China (2019KJC004)+1 种基金the Outstanding Youth Foundation of Shandong Province, China (ZR2019JQ14)the Taishan Scholar Young Talent Program, Major Scientific and Technological Innovation Project (2019JZZY020405)。
文摘Lithium (Li) metal batteries have attracted much attention owing to its ultra-high energy density.However,as important part of Li metal batteries,Li anodes still face many challenges,mainly including uncontrolled dendritic Li formation,dramatical volume variation and serious pulverization.Herein,manganese dioxide (MnO_(2)) nanosheet modified nitrogen (N),phosphorus (P) co-doping carbon nanofibers(NPC) on carbon cloth (CC)(MnO_(2)@NPC-CC) is successfully fabricated through electrodeposition approach and further treated with Li by the molten-infusion method to prepare Li based Mn@NPC-CC(Li-Mn@NPC-CC) electrode.The synergy of MnO_(2) and NPC obviously increases the reaction rate between MnO_(2)@NPC-CC and Li and guides even Li distribution over infusion process.Additionally,theoretical calculation,simulation and experimental results further indicate that N,P,Mn multi-doping effectively improves the superior lithiophilicity of Li-Mn@NPC-CC,which induces uniform Li deposition/dissolution to suppress dendrite growth over cycles.Moreover,conductive and porous NPC matrix not only effectively improves the stability of Li-Mn@NPC-CC,but also provides abundant spaces to accelerate the transfer of ion/electron and buffer electrode dimension variation during cycling.Hence,Li-Mn@NPC-CC-based symmetric cells exhibit extra-long cycling life (over 2200 h) with small hysteresis of 20 mV.When the LiMn@NPC-CC anode couples with air,Li iron phosphate (LiFePO_(4)),or hard carbon (C) cathode,the assembled full cells exhibit outstanding performance with low hysteresis and stable cycling properties.Especially,the corresponding pouch-typed Li–air cells also exhibit good performance at different bending angles and even power a series of electronic devices.
基金the National Natural Science Foundation of China(21905151 and 51772162)Outstanding Youth Foundation of Shandong Province,China(ZR2019JQ14)+4 种基金the Natural Science Foundation of Shandong Province(ZR2018BB034)Taishan Scholar Young Talent ProgramMajor Scientific and Technological Innovation Project(2019JZZY020405)China Postdoctoral Science Foundation(2019M652499)the State Key Laboratory of Inorganic Synthesis and Preparative Chemistry of Jilin University(2019-23)。
文摘Designing the highly catalytic activity and durable bifunctional catalysts toward oxygen reduction/evolution reaction(ORR/OER) is paramount for metal–air batteries. Metal–organic frameworks(MOFs)-based materials have attracted a great deal of attention as the potential candidate for effectively catalyzing ORR/OER due to their adjustable composition and porous structure. Herein, we first introduce the Mn species into zeolitic-imidazole frameworks(ZIFs) and then further pyrolyze the Mn-containing bimetallic ZIFs to synthesize core-shell-structured Co@Co4N nanoparticles embedded into MnO-modified porous N-doped carbon nanocubes(Co@Co4N/MnO–NC). Co@Co4N/MnO–NC exhibits the outstanding catalytic activity toward ORR and OER which is attributed to its abundant pyridinic/graphitic N and Co4N,the optimized content of MnO species, highly dispersed catalytic sites and porous carbon matrix. As a result, the Co@Co4N/MnO–NC-based Zn–air battery exhibits enhanced performances, including the high discharge capacity(762 mA h gZn-1), large power density(200.5 mW cm-2), stable potential profile over 72 h, low overpotential(<1.0 V) and superior cycling life(2800 cycles). Moreover, the belt-shaped Co@Co4N/MnO–NC cathode-based Zn–air batteries are also designed which exhibit the superb electrochemical properties at different bending/twisting conditions.
基金the National Natural Science Foundation of China(Nos.21971132 and 52072197)Outstanding Youth Foundation of Shandong Province,China(No.ZR2019JQ14)+7 种基金Youth Innovation and Technology Foundation of Shandong Higher Education Institutions,China(No.2019KJC004)Major Scientific and Technological Innovation Project(No.2019JZZY020405)Major Basic Research Program of Natural Science Foundation of Shandong Province(No.ZR2020ZD09)Taishan Scholar Young Talent Program(No.tsqn201909114)the Key Laboratory of Resource Chemistry,Ministry of Education(No.KLRC_ME2101)Scientific and Technological Innovation Promotion Project for Small-medium Enterprises of Shandong Province(No.2022TSGC1257)Major Research Program of Jining City(No.2020ZDZP024)The 111 Project of China(No.D20017).
文摘Lithium (Li)-CO_(2) battery is rising as an attractive energy-storage system with the competence of CO_(2) conversion/fixation. However, its practical development is seriously hindered by the high overpotential. Herein, a rational design on a highly catalytic Li-CO_(2) battery electrode built by graphdiyne powder as a multi-functional laminar scaffold with anchored highly dispersed Ru nanoparticles is explored. The strong interaction between the abundant acetylenic bond sites of graphdiyne scaffold and Ru nanoparticles can effectively promote the electrochemical progress and reduce the voltage polarization. The unique channels architecture of the cathodic catalyst with enough space not only accelerates CO_(2) diffusion and electrons/Li+ transport, but also allows a large amount of accommodation for discharged product (Li2CO3) to assure an advanced capacity. The corresponding Li-CO_(2) battery displays an advanced discharged capacity of 15,030 mAh/g at 500 mA/g, great capacity retention of 8873 mAh/g at 2 A/g, high coulombic efficiency of 97.6% at 500 mA/g and superior life span for 120 cycles with voltage gap of 1.67 V under a restricted capacity of 1000 mAh/g at 500 mA/g. Ex/in-situ studies prove that synergy between Ru nanoparticles and acetylene bonds of GDY can boost the round-trip CO_(2)RR and CO_(2)ER kinetics.
基金The authors acknowledge funding support from the National Natural Science Foundation of China(Nos.21905151 and 51772162)Youth Innovation and Technology Foundation of Shandong Higher Education Institutions,China(No.2019KJC004)+2 种基金Outstanding Youth Foundation of Shandong Province,China(No.ZR2019JQ14)Taishan Scholar Young Talent Program,Major Scientific and Technological Innovation Project(No.2019JZZY020405)the Postdoctoral Science Foundation of China(No.2019M652499).
文摘Lithium(Li)-O_(2)batteries have triggered worldwide interest due to their ultrahigh theoretical energy density.However,it is a long shot for the grand-scale applications of Li-O_(2)battery at current stage owing to its significant polarization,inferior cycling life,and irreversible decomposition of Li2O_(2).Herein,a facile way of preparing the highly dispersed Co-based nanoparticles encapsulated into porous N-doping carbon polyhedral with the low content of Ru modification(LRu@HDCo-NC)is explored through the pyrolysis of Co/Zn based zeolitic imidazole frameworks(ZIFs)containing Ru-based ligands.Even with the very small amount of Ru introduction(1.8%),LRu@HDCo-NC still exhibits the superior oxygen evolution reaction/oxygen reduction reaction(OER/ORR)performance and also inhibits side reactions in Li-O_(2)battery because of the abundant pores,plentiful surface N heteroatoms,and highly dispersed metal-based sites which are induced by the volatilization of Zn,and conductive/stable carbon skeleton derived from ZIFs.When applied in Li-O_(2)batteries,LRu@HDCo-NC cathode delivers a high discharge capacity of 15,973 mAh·g^(-1)at 200 mA·g^(-1),good capacity retention at higher rate(12,362 mAh·g^(-1)at 500 mA·g^(-1))and outstanding stability for>300 cycles with low voltage polarization of<2.3 V under a cut-off capacity of 1,000 mAh·g^(-1)at 500 mA·g^(-1).More critically,a series of ex situ and in situ characterization technologies disclose that the LRu@HDCo-NC cathodes can effectively promote the reversible reactions in Li-O_(2)batteries.
基金supported by the National Natural Science Foundation of China(52272222 and 52072197)the Outstanding Youth Foundation of Shandong Province,China(ZR2019JQ14)+4 种基金the Youth Innovation and Technology Foundation of Shandong Higher Education Institutions,China(2019KJC004)the Natural Science Foundation of Shandong Province,China(ZR2021MB061)the Major Scientific and Technological Innovation Project(2019JZZY020405)Taishan Scholar Young Talent Program(tsqn201909114)the Major Basic Research Program of Natural Science Foundation of Shandong Province(ZR2020ZD09).
文摘清洁能源支撑的电解海水技术是公认的最有前途的未来可持续绿色制氢途径.商用贵金属催化剂储量低、成本昂贵,且在复杂离子环境下容易快速失活的特性,严重阻碍了电解海水技术的工业化发展.本工作通过Ni掺杂Fe团簇催化碳纳米管生长,再气体磷化法,成功构建了一种含Ni掺杂FeP纳米颗粒封端的新型氮掺杂碳纳米管交织结构(NFP@NC).独特的N-CNTs交织网络,以及N-CNTs和Ni掺杂FeP的强相互作用提供了快速的传质途径,提高了气体逸出效率,并显著增强了催化剂稳定性.NFP@NC在10 mA cm^(−2)的电流密度下的析氧反应过电位为280 mV,析氢反应过电位为206 mV,低于大多数报道的铁基催化剂.本研究为构建交织的碳纳米管网络和制备高性能双功能海水电解催化剂提供了一种有效的途径.
