The layeredδ-MnO_(2)(dMO)is an excellent cathode material for rechargeable aqueous zinc-ion batteries owing to its large interlayer distance(~0.7 nm),high capacity,and low cost;however,such cathodes suffer from struc...The layeredδ-MnO_(2)(dMO)is an excellent cathode material for rechargeable aqueous zinc-ion batteries owing to its large interlayer distance(~0.7 nm),high capacity,and low cost;however,such cathodes suffer from structural degradation during the long-term cycling process,leading to capacity fading.In this study,a Co-doped dMO composite with reduced graphene oxide(GC-dMO)is developed using a simple cost-effective hydrothermal method.The degree of disorderness increases owing to the hetero-atom doping and graphene oxide composites.It is demonstrated that layered dMO and GC-dMO undergo a structural transition from K-birnessite to the Zn-buserite phase upon the first discharge,which enhances the intercalation of Zn^(2+)ions,H_(2)O molecules in the layered structure.The GC-dMO cathode exhibits an excellent capacity of 302 mAh g^(-1)at a current density of 100 mAg^(-1)after 100 cycles as compared with the dMO cathode(159 mAhg^(-1)).The excellent electrochemical performance of the GC-dMO cathode owing to Co-doping and graphene oxide sheets enhances the interlayer gap and disorderness,and maintains structural stability,which facilitates the easy reverse intercalation and de-intercalation of Zn^(2+)ions and H_(2)O molecules.Therefore,GC-dMO is a promising cathode material for large-scale aqueous ZIBs.展开更多
以MnSO_4·H_2O为锰源,K_2S_2O_8为氧化剂,制备了4种含有不同层间阳离子(Me,Me=Mg^(2+)、Co^(2+)、Ni^(2+)、Cu^(2+))的buserite型氧化锰(Me-buserites)。采用X射线衍射(XRD)、电感耦合等离子体原子发射(ICP-AES)和N2吸附–脱附(BET...以MnSO_4·H_2O为锰源,K_2S_2O_8为氧化剂,制备了4种含有不同层间阳离子(Me,Me=Mg^(2+)、Co^(2+)、Ni^(2+)、Cu^(2+))的buserite型氧化锰(Me-buserites)。采用X射线衍射(XRD)、电感耦合等离子体原子发射(ICP-AES)和N2吸附–脱附(BET)对制成Me-buserites的晶相结构、元素组成和比表面积进行了表征。采用25 m L间歇式玻璃反应器,考察了Me-buserites催化叔丁基过氧化氢歧化分解反应动力学。反应动力学分析表明:反应底物叔丁基过氧化氢浓度项反应级数为2,Me-buserites形式浓度项反应级数为1,总反应级数为3;表观活化能为56~125 k J/mol。与动力学拟合结果相一致的反应机理是由前置平衡和速控两个反应步骤组成。基于338 K反应温度准二级速率常数和0.5 h反应时间累积O_2体积决定的活性顺序为Cu-buserite>Mg-buserite>Ni-buserite>Co-buserite;在选定反应条件下,所有Mebuserites的叔丁醇选择性均为100%。展开更多
Owing to the features(high safety,inexpensive and environmental friendliness)of aqueous rechargeable Mg-ion batteries(ARMIBs),they have drawn extensive attention in the future energy storage systems.However,the poor M...Owing to the features(high safety,inexpensive and environmental friendliness)of aqueous rechargeable Mg-ion batteries(ARMIBs),they have drawn extensive attention in the future energy storage systems.However,the poor Mg^(2+)migration kinetics during the Mg^(2+)intercalation/extraction still hinders the progress of developing suitable cathode materials.Herein,a layered buserite Mg-Mn oxide(MMO)material with large interlayer space(~9.70A)and low-crystalline structure is studied as a high-performance cathode in ARMIBs.Compared with the counterpart,the Mg^(2+)migration kinetics of the MMO cathode can be enhanced by its unique structure(bigger interlayer spacing and low-crystalline structure).The layered buserite MMO as a high-performance ARMIBs cathode exhibits high Mg storage capacity(50 mAg^(-1):169.3 mAh g^(-1)),excellent rate capability(1000 mAg^(-1):98.3 mAh g^(-1)),and fast Mg^(2+)migration(an average diffusion coefficient:~4.21×10-^(10)cm^(2)s^(-1))in 0.5 M MgCl_(2)aqueous electrolyte.Moreover,the MMO-1//AC full battery achieved a high discharge capacity(100 mAg^(-1):111 mAh g^(-1)),and an ignored fading over 5000 cycles(1000 mAg^(-1)).Therefore,layered Mg-Mn oxide with large interlayer space may break a new path to develop the promising ARMIBs.展开更多
Birnessite occurs in a wide variety of natural environments, and plays animportant role in soil chemistry. A modified Staehli procedure was used to synthesize sodiumbirnessite in an alkali medium by O_2 oxidation. The...Birnessite occurs in a wide variety of natural environments, and plays animportant role in soil chemistry. A modified Staehli procedure was used to synthesize sodiumbirnessite in an alkali medium by O_2 oxidation. The effects of preparative parameters on thesynthesis of birnessite, such as pretreatment on solutions with N2, reaction temperature, O_2 flowrate, fluxion velocity of the reaction suspension, and dehydration conditions were investigated. Thefluxion velocity of the reactive suspension and O_2 flow rate significantly influenced thesynthesis of birnessite. Vigorous stirring raised the fluxion velocity of the reaction suspensionand easily allowed synthesis of pure crystalline birnessite. However pretreatment of the reactingsolutions with N_2 and the reaction temperature had little effect on the synthesis. Diffusion of O_2was the controlling step during the course of oxidation. The optimum synthetic conditions for purebirnessite were: a NaOH to Mn molar ratio of 13.7, an O_2 flow rate of 2 L min^(-1), and oxidationfor 5 hours with vigorous stirring at normal temperatures. The chemical composition of thesynthesized pure birnessite was Na_(0.25)MnO_(2.07)·0.66H_2O.展开更多
Todorokite commonly occurs in Earth surface environments. The factors governing formation of todorokite, such as reaction temperature, metal ions, dissolved O2 and pH, were investigated in this paper. Results showed t...Todorokite commonly occurs in Earth surface environments. The factors governing formation of todorokite, such as reaction temperature, metal ions, dissolved O2 and pH, were investigated in this paper. Results showed that the forming rate of todorokite and its crystallinity decreased with falling reaction temperature, and the effect of temperature was more significant than that of other parameters. Nature of metal ions in the interlayer of buserite precursor and the structure of the buserite precursor obviously affected buserite transformation into todorokite. Weak bonding between the metal ions and MnO6 layer of buserite was favorable to todorokite formation. The rate of todorokite formation was promoted at a lower temperature with appropriate bubbling of O2. The pH in the system slightly influenced the todorokite formation, and todorokite could also be formed in a weak alkali medium or in a slightly acidic medium. Aged buserite pre-cursor more easily form todorokite than the unaged one.展开更多
基金supported by the National Research Foundation of Korea(NRF)grants funded by the Korean Government(NRF-2021R1A4A1030318,NRF-2022R1C1C1011386,NRF-2020M3H4A1A03084258)supported by the"Regional Innovation Strategy(RIS)"through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(MOE)(2021RIS-003)
文摘The layeredδ-MnO_(2)(dMO)is an excellent cathode material for rechargeable aqueous zinc-ion batteries owing to its large interlayer distance(~0.7 nm),high capacity,and low cost;however,such cathodes suffer from structural degradation during the long-term cycling process,leading to capacity fading.In this study,a Co-doped dMO composite with reduced graphene oxide(GC-dMO)is developed using a simple cost-effective hydrothermal method.The degree of disorderness increases owing to the hetero-atom doping and graphene oxide composites.It is demonstrated that layered dMO and GC-dMO undergo a structural transition from K-birnessite to the Zn-buserite phase upon the first discharge,which enhances the intercalation of Zn^(2+)ions,H_(2)O molecules in the layered structure.The GC-dMO cathode exhibits an excellent capacity of 302 mAh g^(-1)at a current density of 100 mAg^(-1)after 100 cycles as compared with the dMO cathode(159 mAhg^(-1)).The excellent electrochemical performance of the GC-dMO cathode owing to Co-doping and graphene oxide sheets enhances the interlayer gap and disorderness,and maintains structural stability,which facilitates the easy reverse intercalation and de-intercalation of Zn^(2+)ions and H_(2)O molecules.Therefore,GC-dMO is a promising cathode material for large-scale aqueous ZIBs.
文摘以MnSO_4·H_2O为锰源,K_2S_2O_8为氧化剂,制备了4种含有不同层间阳离子(Me,Me=Mg^(2+)、Co^(2+)、Ni^(2+)、Cu^(2+))的buserite型氧化锰(Me-buserites)。采用X射线衍射(XRD)、电感耦合等离子体原子发射(ICP-AES)和N2吸附–脱附(BET)对制成Me-buserites的晶相结构、元素组成和比表面积进行了表征。采用25 m L间歇式玻璃反应器,考察了Me-buserites催化叔丁基过氧化氢歧化分解反应动力学。反应动力学分析表明:反应底物叔丁基过氧化氢浓度项反应级数为2,Me-buserites形式浓度项反应级数为1,总反应级数为3;表观活化能为56~125 k J/mol。与动力学拟合结果相一致的反应机理是由前置平衡和速控两个反应步骤组成。基于338 K反应温度准二级速率常数和0.5 h反应时间累积O_2体积决定的活性顺序为Cu-buserite>Mg-buserite>Ni-buserite>Co-buserite;在选定反应条件下,所有Mebuserites的叔丁醇选择性均为100%。
基金financially supported by the Fundamental Research Funds for the Central Universities(NO.2021CDJXDJH003)Guangdong National Technology Co.,Ltd.
文摘Owing to the features(high safety,inexpensive and environmental friendliness)of aqueous rechargeable Mg-ion batteries(ARMIBs),they have drawn extensive attention in the future energy storage systems.However,the poor Mg^(2+)migration kinetics during the Mg^(2+)intercalation/extraction still hinders the progress of developing suitable cathode materials.Herein,a layered buserite Mg-Mn oxide(MMO)material with large interlayer space(~9.70A)and low-crystalline structure is studied as a high-performance cathode in ARMIBs.Compared with the counterpart,the Mg^(2+)migration kinetics of the MMO cathode can be enhanced by its unique structure(bigger interlayer spacing and low-crystalline structure).The layered buserite MMO as a high-performance ARMIBs cathode exhibits high Mg storage capacity(50 mAg^(-1):169.3 mAh g^(-1)),excellent rate capability(1000 mAg^(-1):98.3 mAh g^(-1)),and fast Mg^(2+)migration(an average diffusion coefficient:~4.21×10-^(10)cm^(2)s^(-1))in 0.5 M MgCl_(2)aqueous electrolyte.Moreover,the MMO-1//AC full battery achieved a high discharge capacity(100 mAg^(-1):111 mAh g^(-1)),and an ignored fading over 5000 cycles(1000 mAg^(-1)).Therefore,layered Mg-Mn oxide with large interlayer space may break a new path to develop the promising ARMIBs.
基金Project supported by the National Natural Science Foundation of China (Nos. 40101017 and 40071048) the Senior Visitor Foundation of Chinese Educational Ministry.
文摘Birnessite occurs in a wide variety of natural environments, and plays animportant role in soil chemistry. A modified Staehli procedure was used to synthesize sodiumbirnessite in an alkali medium by O_2 oxidation. The effects of preparative parameters on thesynthesis of birnessite, such as pretreatment on solutions with N2, reaction temperature, O_2 flowrate, fluxion velocity of the reaction suspension, and dehydration conditions were investigated. Thefluxion velocity of the reactive suspension and O_2 flow rate significantly influenced thesynthesis of birnessite. Vigorous stirring raised the fluxion velocity of the reaction suspensionand easily allowed synthesis of pure crystalline birnessite. However pretreatment of the reactingsolutions with N_2 and the reaction temperature had little effect on the synthesis. Diffusion of O_2was the controlling step during the course of oxidation. The optimum synthetic conditions for purebirnessite were: a NaOH to Mn molar ratio of 13.7, an O_2 flow rate of 2 L min^(-1), and oxidationfor 5 hours with vigorous stirring at normal temperatures. The chemical composition of thesynthesized pure birnessite was Na_(0.25)MnO_(2.07)·0.66H_2O.
基金supported by the National Natural Science Foundation of China(Grant No.40403009)by the Research Fund for the Doctoral Program of Higher Education(Grant No.2002050411).
文摘Todorokite commonly occurs in Earth surface environments. The factors governing formation of todorokite, such as reaction temperature, metal ions, dissolved O2 and pH, were investigated in this paper. Results showed that the forming rate of todorokite and its crystallinity decreased with falling reaction temperature, and the effect of temperature was more significant than that of other parameters. Nature of metal ions in the interlayer of buserite precursor and the structure of the buserite precursor obviously affected buserite transformation into todorokite. Weak bonding between the metal ions and MnO6 layer of buserite was favorable to todorokite formation. The rate of todorokite formation was promoted at a lower temperature with appropriate bubbling of O2. The pH in the system slightly influenced the todorokite formation, and todorokite could also be formed in a weak alkali medium or in a slightly acidic medium. Aged buserite pre-cursor more easily form todorokite than the unaged one.
