The notorious"shuttle effect"of polysulfide during charge-discharge process induces grievous capacity fading,while the sluggish polysulfide conversion kinetics significantly hinders the development of practi...The notorious"shuttle effect"of polysulfide during charge-discharge process induces grievous capacity fading,while the sluggish polysulfide conversion kinetics significantly hinders the development of practically viable lithium-sulfur(Li-S)batteries.In this study,a novel ZIF-7@carbon composite with ZIF-7 sheets vertically rooted on carbon cloth was developed as multifunctional interlayer to address these issues.The composite shows directional layered structure with outstanding compactness,and thus can provide massive active sites for accelerated redox reactions.The pore channels are perpendicular to the square surface,resulting in extremely high utilization of one-dimensional channels.Therefore,this structure can not only maintain the structural stability during the charge-discharge process by providing enough space for volume expansion,but also contribute to efficient exposure and utilization of active sites for the physical/chemical adsorption and catalytic conversion of polysulfide.As a result,Li-S batteries with the as-developed interlayer deliver a considerable areal capacity of 4.75 mAh cm^(-2) at an elevated sulfur loading of 5.5 mg cm^(-2),and an impressive cyclability with an extremely low capacity-fading rate of merely 0.04%per cycle over 500 cycles at 1 C.展开更多
Along with the continuous consumption in lithium-ion batteries (LIBs), the price of cobalt is inevitably going up in recent years. Therefore, recycling valuable Co element from spent devices, and boosting its service ...Along with the continuous consumption in lithium-ion batteries (LIBs), the price of cobalt is inevitably going up in recent years. Therefore, recycling valuable Co element from spent devices, and boosting its service efficiency are becoming two indispensable approaches to promote the utilization of Co in various energy conversion/storage devices. Herein, we realize the recovery of Co from spent LIBs and synthesize a three–dimensional (3D) sea-urchin-like cobalt nitride composite material (labeled as CoN-Gr-2), which is used as a bi-functional catalyst for water splitting. Benefiting from the intrinsic high conductivity, larger surface area and unique 3D sea–urchin–like architecture, CoN-Gr-2 shows an excellent electron transfer efficiency, highly exposed active sites as well as the superior mass transport capacity. The CoN-Gr-2 catalyst exhibits low overpotentials of 128.9 mV and 280 mV for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), which are comparable to the commercial 20 wt% Pt/C and RuO_(2) catalysts. Moreover, when adopting CoN-Gr-2 as both anode and cathode materials for overall water splitting (in 1.0 M KOH electrolyte), the assembled cell achieves a current density of 10 mA cm^(−2) at 1.61 V, which almost close to that of Pt/C||RuO_(2) benchmark (1.60 V), demonstrating its superior water-splitting efficiency. Meanwhile, the CoN catalysts exhibit strong chemical interaction with the Gr support, suppressing the aggregation of CoN catalysts and maintains their high activity during HER and OER reactions. So, the cell exhibits a high current retention of 97.3% after 40 h. This work successfully develops an industrial chain from recycling Co wastes in spent energy devices to controllably designing 3D sea-urchin-like CoN-Gr with high water splitting efficiency. Therefore, it could further promote the efficient utilization of valuable Co element in various energy devices.展开更多
Lithium-sulfur(Li-S)batteries hold great promises to serve as next-generation energy storage devices because of their high theoretical energy density and environmental benignity.However,the shuttle effect of the solub...Lithium-sulfur(Li-S)batteries hold great promises to serve as next-generation energy storage devices because of their high theoretical energy density and environmental benignity.However,the shuttle effect of the soluble lithium polysulfides(LiPS)and intrinsic insulating nature of sulfur lead to low sulfur utilization and coulombic efficiency,leading to poor cycling performance.The impeded charge transportation and retard LiPS catalytic conversion also endows the Li-S batteries with sluggish redox reaction,leading to unsatisfied rate capability.In this study,Co-based MOF material ZIF-67 is used as the precursor to prepare Co nano-dots decorated three-dimensional graphene aerogel as sulfur immobilizer.This porous architecture establishes a highly conductive interconnected framework for fast charge/mass transportation.The exposed Co nano-dots serve as active sites to strongly trap LiPS,which endows CoNDs@G with low decomposition energy barrier for fast LiPS conversion reaction and promote the completely Li2 S catalytic transformation.Li-S cells based on the Co-NDs@G cathode exhibits excellent cyclability and a high capacity retention rate of 91.1%in 100 cycles.This strategy offers a new direction to design sulfur immobilizer for accelerated LiPS conversion kinetics of Li-S batteries.展开更多
基金the financial support from the Outstanding Young Talents Project of Hebei High Education Institutions(BJ2019013)the Natural Science Foundation of Hebei Province(B2019202289,B2019202199)+1 种基金the National Natural Science Foundation of China(No.21908039)the “Hundred Talents Program”of Hebei Province(E2019050013)。
文摘The notorious"shuttle effect"of polysulfide during charge-discharge process induces grievous capacity fading,while the sluggish polysulfide conversion kinetics significantly hinders the development of practically viable lithium-sulfur(Li-S)batteries.In this study,a novel ZIF-7@carbon composite with ZIF-7 sheets vertically rooted on carbon cloth was developed as multifunctional interlayer to address these issues.The composite shows directional layered structure with outstanding compactness,and thus can provide massive active sites for accelerated redox reactions.The pore channels are perpendicular to the square surface,resulting in extremely high utilization of one-dimensional channels.Therefore,this structure can not only maintain the structural stability during the charge-discharge process by providing enough space for volume expansion,but also contribute to efficient exposure and utilization of active sites for the physical/chemical adsorption and catalytic conversion of polysulfide.As a result,Li-S batteries with the as-developed interlayer deliver a considerable areal capacity of 4.75 mAh cm^(-2) at an elevated sulfur loading of 5.5 mg cm^(-2),and an impressive cyclability with an extremely low capacity-fading rate of merely 0.04%per cycle over 500 cycles at 1 C.
基金The authors would like to acknowledge financial support provided by the Key National Natural Science Foundation of Yunnan Province(No.2018FA028,NO.2019FD039 and No.2019FY003023)the National Natural Science Foundation of China(No.51474191,No.52064049 and No.21467030)+4 种基金the National Natural Science Foundation of Yunnan Provincial Department of Education(No.2020 J0016)the International Joint Research Center for Advanced Energy Materials of Yunnan Province(202003AE140001)the Key Laboratory of Solid State Ions for Green Energy of Yunnan University(2019)the Postdoctoral Foundation of Department of Human Resources and Social Security of Yunnan Province(No.W8163007)the Program for Outstand Young Talents(2018)of Yunnan University.
文摘Along with the continuous consumption in lithium-ion batteries (LIBs), the price of cobalt is inevitably going up in recent years. Therefore, recycling valuable Co element from spent devices, and boosting its service efficiency are becoming two indispensable approaches to promote the utilization of Co in various energy conversion/storage devices. Herein, we realize the recovery of Co from spent LIBs and synthesize a three–dimensional (3D) sea-urchin-like cobalt nitride composite material (labeled as CoN-Gr-2), which is used as a bi-functional catalyst for water splitting. Benefiting from the intrinsic high conductivity, larger surface area and unique 3D sea–urchin–like architecture, CoN-Gr-2 shows an excellent electron transfer efficiency, highly exposed active sites as well as the superior mass transport capacity. The CoN-Gr-2 catalyst exhibits low overpotentials of 128.9 mV and 280 mV for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), which are comparable to the commercial 20 wt% Pt/C and RuO_(2) catalysts. Moreover, when adopting CoN-Gr-2 as both anode and cathode materials for overall water splitting (in 1.0 M KOH electrolyte), the assembled cell achieves a current density of 10 mA cm^(−2) at 1.61 V, which almost close to that of Pt/C||RuO_(2) benchmark (1.60 V), demonstrating its superior water-splitting efficiency. Meanwhile, the CoN catalysts exhibit strong chemical interaction with the Gr support, suppressing the aggregation of CoN catalysts and maintains their high activity during HER and OER reactions. So, the cell exhibits a high current retention of 97.3% after 40 h. This work successfully develops an industrial chain from recycling Co wastes in spent energy devices to controllably designing 3D sea-urchin-like CoN-Gr with high water splitting efficiency. Therefore, it could further promote the efficient utilization of valuable Co element in various energy devices.
基金the financial support from the Natural Science Foundation of Hebei Province(B2020202069)。
文摘Lithium-sulfur(Li-S)batteries hold great promises to serve as next-generation energy storage devices because of their high theoretical energy density and environmental benignity.However,the shuttle effect of the soluble lithium polysulfides(LiPS)and intrinsic insulating nature of sulfur lead to low sulfur utilization and coulombic efficiency,leading to poor cycling performance.The impeded charge transportation and retard LiPS catalytic conversion also endows the Li-S batteries with sluggish redox reaction,leading to unsatisfied rate capability.In this study,Co-based MOF material ZIF-67 is used as the precursor to prepare Co nano-dots decorated three-dimensional graphene aerogel as sulfur immobilizer.This porous architecture establishes a highly conductive interconnected framework for fast charge/mass transportation.The exposed Co nano-dots serve as active sites to strongly trap LiPS,which endows CoNDs@G with low decomposition energy barrier for fast LiPS conversion reaction and promote the completely Li2 S catalytic transformation.Li-S cells based on the Co-NDs@G cathode exhibits excellent cyclability and a high capacity retention rate of 91.1%in 100 cycles.This strategy offers a new direction to design sulfur immobilizer for accelerated LiPS conversion kinetics of Li-S batteries.
