Zinc manganese oxide(ZMO)system represents a notable family of mixed transition metal oxides(MTMOs)because of their superiority of the high theoretical capacity,adequacy of natural content,and low cost.However,the met...Zinc manganese oxide(ZMO)system represents a notable family of mixed transition metal oxides(MTMOs)because of their superiority of the high theoretical capacity,adequacy of natural content,and low cost.However,the methods to match both the reliable synthesis and the designable construction of large-sized two-dimensional(2D)ZMO nanosheets are still considered as grand challenges.Herein,we have successfully realized the preparation of 2D ZMO nanosheets with large lateral sizes up to~20 mm by simple pyrolysis of 2D metal–organic framework(MOF)nanosheets precursor.The growth mechanism of 2D MOF is proposed to be based on the lamellar micelles formed by polyvinyl pyrrolidone(PVP).The obtained 2D and porous ZMO nanosheets exhibit high specific capacity as well as good rate capability.More importantly,the as-prepared ZMO electrode shows a remarkable capacity increment upon cycling(from 832 mAh g^(-1) at the 2nd cycle to 1418 mAh g^(-1) at the 700th cycle,at 1 A g^(-1)).Through simple adjustment of the calcination temperature,the valence state of Mn species in the yielding ZMO samples can be fine-tuned.Through systematic investigation towards these ZMOs containing different Mn species,the extra specific capacity is revealed to be chiefly on account of the arising of the valence state of Mn upon the cycling process.Moreover,it is disclosed that the higher-valent Mn the pristine ZMO contains,the more additional capacity it gains upon cycling.We believe that this work will inspire more detailed analysis on the relationship between the valence state of Mn and extra capacity.展开更多
Comprehensive utilization of low grade manganese?zinc compound ore containing lead and silver with a method of reductive acid leaching was studied.According to theφ?pH diagram of Mn?Zn?H2O system,Mn and Zn can be lea...Comprehensive utilization of low grade manganese?zinc compound ore containing lead and silver with a method of reductive acid leaching was studied.According to theφ?pH diagram of Mn?Zn?H2O system,Mn and Zn can be leached simultaneously in the pH range of?2to5.61.The results showed that both hydrogen peroxide and sucrose were effective reductants which could intensify the simultaneous leaching of Mn and Zn into leachate as well as enrich Pb and Ag in the residue.95.88%of Mn and99.23%of Zn were extracted when the compound ore was leached with hydrogen peroxide in sulfuric acid media,meanwhile the contents of Pb and Ag in the residue were enriched to13.21%and489.36g/t,respectively.When sucrose was used as the reductant,the leaching efficiencies of Mn and Zn separately achieved98.26%and99.62%,and contents of Pb and Ag in the residue were as high as13.92%and517.87g/t,respectively.展开更多
In order to optimize and select the appropriate binder to improve the electrochemical performance of aqueous zinc-manganese batteries,the influences of water-soluble binders and oil-based binders on the zinc storage p...In order to optimize and select the appropriate binder to improve the electrochemical performance of aqueous zinc-manganese batteries,the influences of water-soluble binders and oil-based binders on the zinc storage performance of manganese-based cathode materials were systematically investigated.The results show that the water-soluble binders with large numbers of hydroxyl and carboxyl groups are easily soluble in aqueous electrolytes,leading to poor electrochemical performance.Fortunately,the cathodes with polyvinylidene fluoride-hexafluoropropylene(PVDF-HFP)binder display high specific capacity of 264.9 mA·h/g and good capacity retention of 92%after 90 cycles at 100 mA/g.Meanwhile,PVDF-HFP binder with plenty of hydrophobic groups presents excellent ability in inhibiting cracks on the surface of electrode,reducing voltage polarization and charge transfer resistance,as well as maintaining electrode integrity.展开更多
There is an urgent need for low-cost,high-energy-density,environmentally friendly energy storage devices to fulfill the rapidly increasing need for electrical energy storage.Multi-electron redox is considerably crucia...There is an urgent need for low-cost,high-energy-density,environmentally friendly energy storage devices to fulfill the rapidly increasing need for electrical energy storage.Multi-electron redox is considerably crucial for the development of high-energy-density cathodes.Here we present highperformance aqueous zinc-manganese batteries with reversible Mn2+/Mn4+ double redox.The active Mn4+is generated in situ from the Mn2+-containing MnOx nanoparticles and electrolyte.Benefitting from the low crystallinity of the birnessite-type MnO2 as well as the electrolyte with Mn2+additive,the MnOX cathode achieves an ultrahigh energy density with a peak of845.1 Wh kg-1 and an ultralong lifespan of 1500 cycles.The combination of electrochemical measurements and material characterization reveals the reversible Mn2+/Mn4+double redox(birnessite-type MnO2? monoclinic MnOOH and spinel ZnMn2O4 H?Mn2+ions).The reversible Mn2+/Mn4+double redox electrode reaction mechanism offers new opportunities for the design of low-cost,high-energy-density cathodes for advanced rechargeable aqueous batteries.展开更多
The structures of the Mn-Zn ferrites synthesized under different sintering conditions by the sol-gel method were investigated by the X-ray diffraction (XRD) and the scanning electron microscopy (SEM) with focus on...The structures of the Mn-Zn ferrites synthesized under different sintering conditions by the sol-gel method were investigated by the X-ray diffraction (XRD) and the scanning electron microscopy (SEM) with focus on two factors: the pre-sintering treatment and the calcining time. The results show that the sintering conditions have significant effects on the structures and the particle size of the Mn-Zn ferrites. Compared with the products without pre-sintering, those pre-sintered at 500℃ have a single phase and no diffraction peaks of Fe2O3 that could be found. The effects of the pre-sintering temperature on the structures of the ferrites were also studied. As a result, 500℃ proves to be the favorite in the pre-sintering treatment. The XRD patterns of the ferrites calcined at 1 200℃ for 6 h will present diffraction peaks of pure crystallization of spinel phase while those for 2 h or 4 h will show peaks of Fe2O3. The SEM also bears witness to well-grown grains of pure Mn-Zn ferrites if calcined for 6 hours.展开更多
Cadmium (Cd) is a toxic metal with high mobility from soil and known translocation into plants (Song et al., 2015).Because the main source of human exposure to Cd is from food consumption, there has been increased res...Cadmium (Cd) is a toxic metal with high mobility from soil and known translocation into plants (Song et al., 2015).Because the main source of human exposure to Cd is from food consumption, there has been increased research examining Cd uptake in agricultural plants (Li et al., 2014;Rizwan et al., 2016;Song et al., 2015).展开更多
基金This project is financially supported by National Natural Science Foundation of China(Grant No.51502060)Natural Science Foundation of Shandong Province,China(Grant No.ZR2015EQ010 and No.ZR2019MB027)the Fundamental Research Funds for the Central Universities(Grant No.2015DXGJMS004).
文摘Zinc manganese oxide(ZMO)system represents a notable family of mixed transition metal oxides(MTMOs)because of their superiority of the high theoretical capacity,adequacy of natural content,and low cost.However,the methods to match both the reliable synthesis and the designable construction of large-sized two-dimensional(2D)ZMO nanosheets are still considered as grand challenges.Herein,we have successfully realized the preparation of 2D ZMO nanosheets with large lateral sizes up to~20 mm by simple pyrolysis of 2D metal–organic framework(MOF)nanosheets precursor.The growth mechanism of 2D MOF is proposed to be based on the lamellar micelles formed by polyvinyl pyrrolidone(PVP).The obtained 2D and porous ZMO nanosheets exhibit high specific capacity as well as good rate capability.More importantly,the as-prepared ZMO electrode shows a remarkable capacity increment upon cycling(from 832 mAh g^(-1) at the 2nd cycle to 1418 mAh g^(-1) at the 700th cycle,at 1 A g^(-1)).Through simple adjustment of the calcination temperature,the valence state of Mn species in the yielding ZMO samples can be fine-tuned.Through systematic investigation towards these ZMOs containing different Mn species,the extra specific capacity is revealed to be chiefly on account of the arising of the valence state of Mn upon the cycling process.Moreover,it is disclosed that the higher-valent Mn the pristine ZMO contains,the more additional capacity it gains upon cycling.We believe that this work will inspire more detailed analysis on the relationship between the valence state of Mn and extra capacity.
基金Projects(51574284,51504293)supported by the National Natural Science Foundation of ChinaProject(2013IB020)supported by the Science and Technology Program of Yunnan Province,ChinaProject(CSUZC201606)supported by the Open-End Fund for the Valuable and Precision Instruments of Central South University,China
文摘Comprehensive utilization of low grade manganese?zinc compound ore containing lead and silver with a method of reductive acid leaching was studied.According to theφ?pH diagram of Mn?Zn?H2O system,Mn and Zn can be leached simultaneously in the pH range of?2to5.61.The results showed that both hydrogen peroxide and sucrose were effective reductants which could intensify the simultaneous leaching of Mn and Zn into leachate as well as enrich Pb and Ag in the residue.95.88%of Mn and99.23%of Zn were extracted when the compound ore was leached with hydrogen peroxide in sulfuric acid media,meanwhile the contents of Pb and Ag in the residue were enriched to13.21%and489.36g/t,respectively.When sucrose was used as the reductant,the leaching efficiencies of Mn and Zn separately achieved98.26%and99.62%,and contents of Pb and Ag in the residue were as high as13.92%and517.87g/t,respectively.
基金supported by the National Natural Science Foundation of China (Nos.51932011, 51972346)the Hunan Natural Science Fund for Distinguished Young Scholar, China (No. 2021JJ10064)+1 种基金the Program of Youth Talent Support for Hunan Province, China (No. 2020RC3011)the Innovation-Driven Project of Central South University, China (No. 2020CX024)
文摘In order to optimize and select the appropriate binder to improve the electrochemical performance of aqueous zinc-manganese batteries,the influences of water-soluble binders and oil-based binders on the zinc storage performance of manganese-based cathode materials were systematically investigated.The results show that the water-soluble binders with large numbers of hydroxyl and carboxyl groups are easily soluble in aqueous electrolytes,leading to poor electrochemical performance.Fortunately,the cathodes with polyvinylidene fluoride-hexafluoropropylene(PVDF-HFP)binder display high specific capacity of 264.9 mA·h/g and good capacity retention of 92%after 90 cycles at 100 mA/g.Meanwhile,PVDF-HFP binder with plenty of hydrophobic groups presents excellent ability in inhibiting cracks on the surface of electrode,reducing voltage polarization and charge transfer resistance,as well as maintaining electrode integrity.
基金supported by the National Natural Science Foundation of China(Grant No.51772331)the National Key Technologies R&D Program(Grant No.2018YFB1106000).
文摘There is an urgent need for low-cost,high-energy-density,environmentally friendly energy storage devices to fulfill the rapidly increasing need for electrical energy storage.Multi-electron redox is considerably crucial for the development of high-energy-density cathodes.Here we present highperformance aqueous zinc-manganese batteries with reversible Mn2+/Mn4+ double redox.The active Mn4+is generated in situ from the Mn2+-containing MnOx nanoparticles and electrolyte.Benefitting from the low crystallinity of the birnessite-type MnO2 as well as the electrolyte with Mn2+additive,the MnOX cathode achieves an ultrahigh energy density with a peak of845.1 Wh kg-1 and an ultralong lifespan of 1500 cycles.The combination of electrochemical measurements and material characterization reveals the reversible Mn2+/Mn4+double redox(birnessite-type MnO2? monoclinic MnOOH and spinel ZnMn2O4 H?Mn2+ions).The reversible Mn2+/Mn4+double redox electrode reaction mechanism offers new opportunities for the design of low-cost,high-energy-density cathodes for advanced rechargeable aqueous batteries.
文摘The structures of the Mn-Zn ferrites synthesized under different sintering conditions by the sol-gel method were investigated by the X-ray diffraction (XRD) and the scanning electron microscopy (SEM) with focus on two factors: the pre-sintering treatment and the calcining time. The results show that the sintering conditions have significant effects on the structures and the particle size of the Mn-Zn ferrites. Compared with the products without pre-sintering, those pre-sintered at 500℃ have a single phase and no diffraction peaks of Fe2O3 that could be found. The effects of the pre-sintering temperature on the structures of the ferrites were also studied. As a result, 500℃ proves to be the favorite in the pre-sintering treatment. The XRD patterns of the ferrites calcined at 1 200℃ for 6 h will present diffraction peaks of pure crystallization of spinel phase while those for 2 h or 4 h will show peaks of Fe2O3. The SEM also bears witness to well-grown grains of pure Mn-Zn ferrites if calcined for 6 hours.
文摘Cadmium (Cd) is a toxic metal with high mobility from soil and known translocation into plants (Song et al., 2015).Because the main source of human exposure to Cd is from food consumption, there has been increased research examining Cd uptake in agricultural plants (Li et al., 2014;Rizwan et al., 2016;Song et al., 2015).