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© 2020, Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature. Ti-based anode materials in sodium ion batteries have attracted extensive interests due to its abundant resources, low toxicity, easy synthesis and long cycle life. However, low Coulombic efficiency and limited specific capacity affect their applications. Here, cubic-phase TiP2O7 is examined as anode materials, using in-situ/ex-situ characterization techniques. It is concluded that the redox reactions of Ti4+/Ti3+ and Ti3+/Ti0 consecutively occur during the discharge/charge processes, both of which are highly reversible. These reactions make the specific capacity of TiP2O7 even higher than the case of TiO2 that only contains a simple anion, O2−. Interestingly, Ti species participate only one of the redox reactions, due to the remarkable difference in local structures related to the sodiation process. The stable discharge/charge products in TiP2O7 reduce the side reactions and improve the Coulombic efficiency as compared to TiO2. These features make it a promising Ti-based anode for sodium ion batteries. Therefore, TiP2O7@C microflowers exhibit excellent electrochemical performances, ~ 109 mAh·g−1 after 10,000 cycles at 2 A·g−1, or 95.2 mAh·g−1 at 10 A·g−1. The results demonstrate new opportunities for advanced Ti-based anodes in sodium ion batteries. [Figure not available: see fulltext.]

© 2020, Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature. Ti-based anode materials in sodium ion batteries have attracted extensive interests due to its abundant resources, low toxicity, easy synthesis and long cycle life. However, low Coulombic efficiency and limited specific capacity affect their applications. Here, cubic-phase TiP2O7 is examined as anode materials, using in-situ/ex-situ characterization techniques. It is concluded that the redox reactions of Ti4+/Ti3+ and Ti3+/Ti0 consecutively occur during the discharge/charge processes, both of which are highly reversible. These reactions make the specific capacity of TiP2O7 even higher than the case of TiO2 that only contains a simple anion, O2−. Interestingly, Ti species participate only one of the redox reactions, due to the remarkable difference in local structures related to the sodiation process. The stable discharge/charge products in TiP2O7 reduce the side reactions and improve the Coulombic efficiency as compared to TiO2. These features make it a promising Ti-based anode for sodium ion batteries. Therefore, TiP2O7@C microflowers exhibit excellent electrochemical performances, ~ 109 mAh·g−1 after 10,000 cycles at 2 A·g−1, or 95.2 mAh·g−1 at 10 A·g−1. The results demonstrate new opportunities for advanced Ti-based anodes in sodium ion batteries. [Figure not available: see fulltext.]

We present a general strategy to synthesize uniform MnCo2O4 submicrospheres with various hollow structures. By using MnCo-glycolate submicrospheres as the precursor with proper manipulation of ramping rates during the heating process, we have fabricated hollow MnCo2O4 submicrospheres with multilevel interiors, including mesoporous spheres, hollow spheres, yolk-shell spheres, shell-in-shell spheres, and yolk-in-double-shell spheres. Interestingly, when tested as anode materials in lithium ion batteries, the MnCo2O4 submicrospheres with a yolk-shell structure showed the best performance among these multilevel interior structures because these structures can not only supply a high contact area but also maintain a stable structure.

We present a general strategy to synthesize uniform MnCo2O4 submicrospheres with various hollow structures. By using MnCo-glycolate submicrospheres as the precursor with proper manipulation of ramping rates during the heating process, we have fabricated hollow MnCo2O4 submicrospheres with multilevel interiors, including mesoporous spheres, hollow spheres, yolk-shell spheres, shell-in-shell spheres, and yolk-in-double-shell spheres. Interestingly, when tested as anode materials in lithium ion batteries, the MnCo2O4 submicrospheres with a yolk-shell structure showed the best performance among these multilevel interior structures because these structures can not only supply a high contact area but also maintain a stable structure.

We present a general strategy to synthesize uniform MnCo2O4 submicrospheres with various hollow structures. By using MnCo-glycolate submicrospheres as the precursor with proper manipulation of ramping rates during the heating process, we have fabricated hollow MnCo2O4 submicrospheres with multilevel interiors, including mesoporous spheres, hollow spheres, yolk-shell spheres, shell-in-shell spheres, and yolk-in-double-shell spheres. Interestingly, when tested as anode materials in lithium ion batteries, the MnCo2O4 submicrospheres with a yolk-shell structure showed the best performance among these multilevel interior structures because these structures can not only supply a high contact area but also maintain a stable structure.

We present a general strategy to synthesize uniform MnCo2O4 submicrospheres with various hollow structures. By using MnCo-glycolate submicrospheres as the precursor with proper manipulation of ramping rates during the heating process, we have fabricated hollow MnCo2O4 submicrospheres with multilevel interiors, including mesoporous spheres, hollow spheres, yolk-shell spheres, shell-in-shell spheres, and yolk-in-double-shell spheres. Interestingly, when tested as anode materials in lithium ion batteries, the MnCo2O4 submicrospheres with a yolk-shell structure showed the best performance among these multilevel interior structures because these structures can not only supply a high contact area but also maintain a stable structure.

We present a general strategy to synthesize uniform MnCo2O4 submicrospheres with various hollow structures. By using MnCo-glycolate submicrospheres as the precursor with proper manipulation of ramping rates during the heating process, we have fabricated hollow MnCo2O4 submicrospheres with multilevel interiors, including mesoporous spheres, hollow spheres, yolk-shell spheres, shell-in-shell spheres, and yolk-in-double-shell spheres. Interestingly, when tested as anode materials in lithium ion batteries, the MnCo2O4 submicrospheres with a yolk-shell structure showed the best performance among these multilevel interior structures because these structures can not only supply a high contact area but also maintain a stable structure.

A facile method is presented for the large-scale preparation of rationally designed mesocrystalline MnO@carbon core-shell nanowires with a jointed appearance. The nanostructures have a unique arrangement of internally encapsulated highly oriented and interconnected MnO nanorods and graphitized carbon layers forming an external coating. Based on a comparison and analysis of the crystal structures of MnOOH, Mn2O3, and MnO@C, we propose a sequential topotactic transformation of the corresponding precursors to the products. Very interestingly, the individual mesoporous single-crystalline MnO nanorods are strongly interconnected and maintain the same crystallographic orientation, which is a typical feature of mesocrystals. When tested for their applicability to Li-ion batteries (LIB), the MnO@carbon core-shell nanowires showed excellent capacity retention, superior cycling performance, and high rate capability. Specifically, the MnO@carbon core-shell nanostructures could deliver reversible capacities as high as 801 mA h g -1 at a high current density of 500 mA g-1, with excellent electrochemical stability after testing over 200 cycles, indicating their potential application in LIBs. The remarkable electrochemical performance can mainly be attributed to the highly uniform carbon layer around the MnO nanowires, which is not only effective in buffering the structural strain and volume variations of anodes during repeated electrochemical reactions, but also greatly enhances the conductivity of the electrode material. Our results confirm the feasibility of using these rationally designed composite materials for practical applications. The present strategy is simple but very effective, and appears to be sufficiently versatile to be extended to other high-capacity electrode materials with large volume variations and low electrical conductivities.

A facile method is presented for the large-scale preparation of rationally designed mesocrystalline MnO@carbon core-shell nanowires with a jointed appearance. The nanostructures have a unique arrangement of internally encapsulated highly oriented and interconnected MnO nanorods and graphitized carbon layers forming an external coating. Based on a comparison and analysis of the crystal structures of MnOOH, Mn2O3, and MnO@C, we propose a sequential topotactic transformation of the corresponding precursors to the products. Very interestingly, the individual mesoporous single-crystalline MnO nanorods are strongly interconnected and maintain the same crystallographic orientation, which is a typical feature of mesocrystals. When tested for their applicability to Li-ion batteries (LIB), the MnO@carbon core-shell nanowires showed excellent capacity retention, superior cycling performance, and high rate capability. Specifically, the MnO@carbon core-shell nanostructures could deliver reversible capacities as high as 801 mA h g -1 at a high current density of 500 mA g-1, with excellent electrochemical stability after testing over 200 cycles, indicating their potential application in LIBs. The remarkable electrochemical performance can mainly be attributed to the highly uniform carbon layer around the MnO nanowires, which is not only effective in buffering the structural strain and volume variations of anodes during repeated electrochemical reactions, but also greatly enhances the conductivity of the electrode material. Our results confirm the feasibility of using these rationally designed composite materials for practical applications. The present strategy is simple but very effective, and appears to be sufficiently versatile to be extended to other high-capacity electrode materials with large volume variations and low electrical conductivities.

Mixed metal oxides have been attracting more and more attention recently because of their advantages and superiorities, which can improve the electrochemical performance of single metal oxides. These advantages include structural stability, good electronic conductivity, and reversible capacity. In this work, uniform yolk-shelled ZnCo2O4 microspheres were synthesized by pyrolysis of ZnCo-glycolate microsphere precursors which were prepared via a simple refluxing route without any precipitant or surfactant. The formation process of the yolk-shelled microsphere structure during the thermal decomposition of ZnCo-glycolate is discussed, which is mainly based on the heterogeneous contraction caused by non-equilibrium heat treatment. The performances of the as-prepared ZnCo2O4 electrodes using sodium carboxylmethyl cellulose (CMC) and poly-vinylidene fluoride (PVDF) as binders are also compared. Constant current and rate charge–discharge testing results demonstrated that the ZnCo2O4 electrodes using CMC as the binder had better performance than those using PVDF as the binder. It was worth pointing out that the electrode using CMC as the binder nicely yields a discharge capacity of 331 mA h g−1 after 500 cycles at a current density of 1000 mA g−1, which is close to the theoretical value of graphite (371 mA h g−1). Furthermore, the obtained synthetic insights on the complex hollow structures will be of benefit to the design of other anode materials for lithium ion batteries.

Mixed metal oxides have been attracting more and more attention recently because of their advantages and superiorities, which can improve the electrochemical performance of single metal oxides. These advantages include structural stability, good electronic conductivity, and reversible capacity. In this work, uniform yolk-shelled ZnCo2O4 microspheres were synthesized by pyrolysis of ZnCo-glycolate microsphere precursors which were prepared via a simple refluxing route without any precipitant or surfactant. The formation process of the yolk-shelled microsphere structure during the thermal decomposition of ZnCo-glycolate is discussed, which is mainly based on the heterogeneous contraction caused by non-equilibrium heat treatment. The performances of the as-prepared ZnCo2O4 electrodes using sodium carboxylmethyl cellulose (CMC) and poly-vinylidene fluoride (PVDF) as binders are also compared. Constant current and rate charge–discharge testing results demonstrated that the ZnCo2O4 electrodes using CMC as the binder had better performance than those using PVDF as the binder. It was worth pointing out that the electrode using CMC as the binder nicely yields a discharge capacity of 331 mA h g−1 after 500 cycles at a current density of 1000 mA g−1, which is close to the theoretical value of graphite (371 mA h g−1). Furthermore, the obtained synthetic insights on the complex hollow structures will be of benefit to the design of other anode materials for lithium ion batteries.

Mixed metal oxides have been attracting more and more attention recently because of their advantages and superiorities, which can improve the electrochemical performance of single metal oxides. These advantages include structural stability, good electronic conductivity, and reversible capacity. In this work, uniform yolk-shelled ZnCo2O4 microspheres were synthesized by pyrolysis of ZnCo-glycolate microsphere precursors which were prepared via a simple refluxing route without any precipitant or surfactant. The formation process of the yolk-shelled microsphere structure during the thermal decomposition of ZnCo-glycolate is discussed, which is mainly based on the heterogeneous contraction caused by non-equilibrium heat treatment. The performances of the as-prepared ZnCo2O4 electrodes using sodium carboxylmethyl cellulose (CMC) and poly-vinylidene fluoride (PVDF) as binders are also compared. Constant current and rate charge–discharge testing results demonstrated that the ZnCo2O4 electrodes using CMC as the binder had better performance than those using PVDF as the binder. It was worth pointing out that the electrode using CMC as the binder nicely yields a discharge capacity of 331 mA h g−1 after 500 cycles at a current density of 1000 mA g−1, which is close to the theoretical value of graphite (371 mA h g−1). Furthermore, the obtained synthetic insights on the complex hollow structures will be of benefit to the design of other anode materials for lithium ion batteries.

A facile method is presented for the large-scale preparation of rationally designed mesocrystalline MnO@carbon core-shell nanowires with a jointed appearance. The nanostructures have a unique arrangement of internally encapsulated highly oriented and interconnected MnO nanorods and graphitized carbon layers forming an external coating. Based on a comparison and analysis of the crystal structures of MnOOH, Mn2O3, and MnO@C, we propose a sequential topotactic transformation of the corresponding precursors to the products. Very interestingly, the individual mesoporous single-crystalline MnO nanorods are strongly interconnected and maintain the same crystallographic orientation, which is a typical feature of mesocrystals. When tested for their applicability to Li-ion batteries (LIB), the MnO@carbon core-shell nanowires showed excellent capacity retention, superior cycling performance, and high rate capability. Specifically, the MnO@carbon core-shell nanostructures could deliver reversible capacities as high as 801 mA h g -1 at a high current density of 500 mA g-1, with excellent electrochemical stability after testing over 200 cycles, indicating their potential application in LIBs. The remarkable electrochemical performance can mainly be attributed to the highly uniform carbon layer around the MnO nanowires, which is not only effective in buffering the structural strain and volume variations of anodes during repeated electrochemical reactions, but also greatly enhances the conductivity of the electrode material. Our results confirm the feasibility of using these rationally designed composite materials for practical applications. The present strategy is simple but very effective, and appears to be sufficiently versatile to be extended to other high-capacity electrode materials with large volume variations and low electrical conductivities.

Mixed metal oxides have been attracting more and more attention recently because of their advantages and superiorities, which can improve the electrochemical performance of single metal oxides. These advantages include structural stability, good electronic conductivity, and reversible capacity. In this work, uniform yolk-shelled ZnCo2O4 microspheres were synthesized by pyrolysis of ZnCo-glycolate microsphere precursors which were prepared via a simple refluxing route without any precipitant or surfactant. The formation process of the yolk-shelled microsphere structure during the thermal decomposition of ZnCo-glycolate is discussed, which is mainly based on the heterogeneous contraction caused by non-equilibrium heat treatment. The performances of the as-prepared ZnCo2O4 electrodes using sodium carboxylmethyl cellulose (CMC) and poly-vinylidene fluoride (PVDF) as binders are also compared. Constant current and rate charge–discharge testing results demonstrated that the ZnCo2O4 electrodes using CMC as the binder had better performance than those using PVDF as the binder. It was worth pointing out that the electrode using CMC as the binder nicely yields a discharge capacity of 331 mA h g−1 after 500 cycles at a current density of 1000 mA g−1, which is close to the theoretical value of graphite (371 mA h g−1). Furthermore, the obtained synthetic insights on the complex hollow structures will be of benefit to the design of other anode materials for lithium ion batteries.

A facile method is presented for the large-scale preparation of rationally designed mesocrystalline MnO@carbon core-shell nanowires with a jointed appearance. The nanostructures have a unique arrangement of internally encapsulated highly oriented and interconnected MnO nanorods and graphitized carbon layers forming an external coating. Based on a comparison and analysis of the crystal structures of MnOOH, Mn2O3, and MnO@C, we propose a sequential topotactic transformation of the corresponding precursors to the products. Very interestingly, the individual mesoporous single-crystalline MnO nanorods are strongly interconnected and maintain the same crystallographic orientation, which is a typical feature of mesocrystals. When tested for their applicability to Li-ion batteries (LIB), the MnO@carbon core-shell nanowires showed excellent capacity retention, superior cycling performance, and high rate capability. Specifically, the MnO@carbon core-shell nanostructures could deliver reversible capacities as high as 801 mA h g -1 at a high current density of 500 mA g-1, with excellent electrochemical stability after testing over 200 cycles, indicating their potential application in LIBs. The remarkable electrochemical performance can mainly be attributed to the highly uniform carbon layer around the MnO nanowires, which is not only effective in buffering the structural strain and volume variations of anodes during repeated electrochemical reactions, but also greatly enhances the conductivity of the electrode material. Our results confirm the feasibility of using these rationally designed composite materials for practical applications. The present strategy is simple but very effective, and appears to be sufficiently versatile to be extended to other high-capacity electrode materials with large volume variations and low electrical conductivities.

Single-crystalline zinc selenide (ZnSe) nanobelts were fabricated via the ethylenediamine (en)-assisted ternary solution technique and subsequent thermal treatment. Individual ZnSe nanobelts were assembled into nanoscale devices, showing a high spectral selectivity and photocurrent/immediate-decay ratio and a fast time response, justifying effective utilization of the ZnSe nanobelts as blue/UV-light-sensitive photodetectors.

Sb2S3 nanowires with high aspect ratios have been successfully prepared on a large scale using SbCl3 and Na2S as starting materials in ethylene glycol at 200°C for 10 h. Field emission scanning electron microscopy images and transmission electron microscopy images show that the nanowires have diameters in the range of 20–100 nm and lengths up to 50 μm. Diffuse reflection spectrum indicates that the as-prepared Sb2S3 nanowires have obvious quantum size effects. The effects of reaction parameters on the growth of nanowires were discussed. A possible mechanism on the formation of the Sb2S3 nanowires was proposed.