The desire for practical utilization of rechargeable lithium batteries with high energy density has motivated attempts to develop new electrode materials and battery systems. Here, without additional binders we presen...The desire for practical utilization of rechargeable lithium batteries with high energy density has motivated attempts to develop new electrode materials and battery systems. Here, without additional binders we present a simple vacuum filtration method to synthesize nitrogen and sulfur codoped graphene(N,S-G) blocking layer, which is ultra-lightweight, conductive, and free standing. When the N,S-G membrane was inserted between the catholyte and separator, the lithium–selenium(Li–Se)batteries exhibited a high reversible discharge capacity of 330.7 mAh g^(-1) at 1 C(1 C = 675 mA g^(-1)) after 500 cycles and high rate performance(over 310 mAh g^(-1) at 4 C) even at an active material loading as high as ～5 mg cm^(-2). This excellent performance can be ascribed to homogenous dispersion of the liquid active material in the electrode, good Li^+-ion conductivity, fast electronic transport in the conductive graphene framework, andstrong chemical confinement of polyselenides by nitrogen and sulfur atoms. More importantly, it is a promising strategy for enhancing the energy density of Li–Se batteries by using the catholyte with a lightweight heteroatom doping carbon matrix.展开更多
本文以南瓜为前驱体,通过“水热反应-KOH活化-碳化”制备工艺,制备得到多孔碳材料(429.85 m^2 g^-1)。再通过封闭空间高温烧结的方法,将单质Se熔解-扩散进入多孔C材料中,同时控制活性物质Se的尺寸和形貌,进一步提高Se负载率(51.8%),从...本文以南瓜为前驱体,通过“水热反应-KOH活化-碳化”制备工艺,制备得到多孔碳材料(429.85 m^2 g^-1)。再通过封闭空间高温烧结的方法,将单质Se熔解-扩散进入多孔C材料中,同时控制活性物质Se的尺寸和形貌,进一步提高Se负载率(51.8%),从而获得高性能锂-硒电池正极复合材料。得到C/Se复合材料首圈放电容量超过1000 mAh g^-1,并且100圈后仍能维持在400 mAh g^-1左右。本文制备的C/Se复合材料具有良好的孔径结构,并且电化学性能优异,同时原料来源广泛且廉价,制备工艺简单,为锂-硒电池产业化提供了更大的可能。展开更多
锂-硒电池因其超高的体积能量密度和硒的高电导率而被认为是一种极具有发展前景的锂离子电池。然而,循环过程中电极严重的体积膨胀和多硒化物溶解,以及硒的低负载,阻碍了锂-硒电池应用的发展。解决这三个问题的一种行之有效的方法是将...锂-硒电池因其超高的体积能量密度和硒的高电导率而被认为是一种极具有发展前景的锂离子电池。然而,循环过程中电极严重的体积膨胀和多硒化物溶解,以及硒的低负载,阻碍了锂-硒电池应用的发展。解决这三个问题的一种行之有效的方法是将硒限制在具有丰富孔体积的碳基质中,并同时增强硒与碳的界面相互作用。通过将Se浸入酒石酸盐衍生的蜂窝状三维多孔炭中,合成出了一种具有Se―C键的蜂窝状三维多孔炭@硒(HPC@Se)的新型正极材料用于锂-Se电池。得到的蜂窝状三维多孔炭的孔体积可达1.794 cm^(3)g^(-1),能够均匀包封65%硒。此外,硒与碳之间的强化学键有利于稳定硒,从而进一步缓解其巨大的体积膨胀和多硒化物的溶解,还可促进循环过程中的电荷转移。该HPC@Se正极呈现出极好的循环性能和倍率性能。在0.2 C的电流密度下,经200次循环后,其比容量可保持在561 m Ahg^(-1)(为理论比容量的83%),每次循环的比容量衰减率仅为0.058%。此外,在5 C的高电流密度下,HPC@Se正极还可以达到472.8 m Ahg^(-1)的可观容量。展开更多
Li–S and Li–Se batteries have attracted tremendous attention during the past several decades, as the energy density of Li–S and Li–Se batteries is high（several times higher than that of traditional Li-ion batter...Li–S and Li–Se batteries have attracted tremendous attention during the past several decades, as the energy density of Li–S and Li–Se batteries is high（several times higher than that of traditional Li-ion batteries）.Besides, Li–S and Li–Se batteries are low cost and environmental benign. However, the commercial applications of Li–S and Li–Se batteries are hindered by the dissolution and shuttle phenomena of polysulfide（polyselenium）, the low conductivity of S（Se）, etc. To overcome these drawbacks, scientists have come up with various methods, such as optimizing the electrolyte, synthesizing composite electrode of S/polymer, S/carbon, S/metal organic framework（MOF） and constructing novelty structure of battery.In this review, we present a systematic introduction about the recent progress of Li–S and Li–Se batteries, especially in the area of electrode materials, both of cathode material and anode material for Li–S and Li–Se batteries. In addition, other methods to lead a high-performance Li–S and Li–Se batteries are also briefly summarized, such as constructing novelty battery structure, adopting proper charge–discharge conditions, heteroatom doping into sulfur molecules, using different kinds of electrolytes and binders. In the end of the review, the developed directions of Li–S and Li–Se batteries are also pointed out. We believe that combining proper porous carbon matrix and heteroatom doping may further improve the electrochemical performance of Li–S and Li–Se batteries. We also believe that Li–S and Li–Se batteries will get more exciting results and have promising future by the effort of battery community.展开更多
A dual functional CNTs@graphene/CNTs cathode for Li–Se battery was constructed by a CNTs@graphene network and a CNTs interlayer. CNTs were first integrated with graphene to form a three-dimensional（3D） framework an...A dual functional CNTs@graphene/CNTs cathode for Li–Se battery was constructed by a CNTs@graphene network and a CNTs interlayer. CNTs were first integrated with graphene to form a three-dimensional（3D） framework and work together as a conductive matrix for Se confinement. The optimized composite cathode delivers a high initial capacity of 575 mAh·g^-1 at 0.5 A·g^-1 and good rate capacity with a retained capacity of 479 mAh·g^-1 at 2.0 A·g^-1（73% of the capacity at 0.2 A·g^-1）. CNTs were further served as an interlayer to confine the diffusion of polyselenides by constructing a thin CNTs layer outside the CNTs@graphene network. An improved initial capacity of 616 mAh·g^-1 at 0.5 A·g^-1 is achieved with a retained capacity of 538 mAh·g^-1 after 80 cycles, indicating the effective dual function of CNTs in this novel cathode construction and great application potential for Li–Se battery.展开更多
Animal bone was employed as raw material to prepare hierarchical porous carbon by KOH activation. Rare metal selenium（Se） was encapsulated into hierarchical porous carbon successfully for the cathode material of Li...Animal bone was employed as raw material to prepare hierarchical porous carbon by KOH activation. Rare metal selenium（Se） was encapsulated into hierarchical porous carbon successfully for the cathode material of Li–Se battery, achieving the transformation of waste into energy,protecting environment and reducing the spread of the disease. Animal bone porous carbon（ABPC） acquires a specific surface area of 1244.7903 m^2·g^-1 and a pore volume of 0.594184 cm^3·g^-1. The composite Se/ABPC with 51 wt%Se was tested as a novel cathode for Li–Se batteries. The results show that Se/ABPC exhibits high specific capacity,good cycling stability and current-rate performance; at 0.1C,the composite Se/ABPC delivers a high reversible capacity of 705 mAh·g^-1 in the second cycle and 591 mAh·g^-1 after 98 cycles. Even at the current density of 2.0C, it can still maintain at a reversible capacity of 485 mAh·g^-1. The excellent electrochemical properties benefit from the high electron conductivity and the carbon with unique hierarchical porous structure. ABPC can be a promising carbon matrix for Li–Se batteries.展开更多
基金supported by the National Natural Science Foundation of China (51125001,51172005)the NSFCRGC Joint Research Scheme (51361165201)the Start-up Foundation of High-level Talents in Chongqing Technology and Business University (1856008)
文摘The desire for practical utilization of rechargeable lithium batteries with high energy density has motivated attempts to develop new electrode materials and battery systems. Here, without additional binders we present a simple vacuum filtration method to synthesize nitrogen and sulfur codoped graphene(N,S-G) blocking layer, which is ultra-lightweight, conductive, and free standing. When the N,S-G membrane was inserted between the catholyte and separator, the lithium–selenium(Li–Se)batteries exhibited a high reversible discharge capacity of 330.7 mAh g^(-1) at 1 C(1 C = 675 mA g^(-1)) after 500 cycles and high rate performance(over 310 mAh g^(-1) at 4 C) even at an active material loading as high as ～5 mg cm^(-2). This excellent performance can be ascribed to homogenous dispersion of the liquid active material in the electrode, good Li^+-ion conductivity, fast electronic transport in the conductive graphene framework, andstrong chemical confinement of polyselenides by nitrogen and sulfur atoms. More importantly, it is a promising strategy for enhancing the energy density of Li–Se batteries by using the catholyte with a lightweight heteroatom doping carbon matrix.
文摘本文以南瓜为前驱体,通过“水热反应-KOH活化-碳化”制备工艺,制备得到多孔碳材料(429.85 m^2 g^-1)。再通过封闭空间高温烧结的方法,将单质Se熔解-扩散进入多孔C材料中,同时控制活性物质Se的尺寸和形貌,进一步提高Se负载率(51.8%),从而获得高性能锂-硒电池正极复合材料。得到C/Se复合材料首圈放电容量超过1000 mAh g^-1,并且100圈后仍能维持在400 mAh g^-1左右。本文制备的C/Se复合材料具有良好的孔径结构,并且电化学性能优异,同时原料来源广泛且廉价,制备工艺简单,为锂-硒电池产业化提供了更大的可能。
文摘锂-硒电池因其超高的体积能量密度和硒的高电导率而被认为是一种极具有发展前景的锂离子电池。然而,循环过程中电极严重的体积膨胀和多硒化物溶解,以及硒的低负载,阻碍了锂-硒电池应用的发展。解决这三个问题的一种行之有效的方法是将硒限制在具有丰富孔体积的碳基质中,并同时增强硒与碳的界面相互作用。通过将Se浸入酒石酸盐衍生的蜂窝状三维多孔炭中,合成出了一种具有Se―C键的蜂窝状三维多孔炭@硒(HPC@Se)的新型正极材料用于锂-Se电池。得到的蜂窝状三维多孔炭的孔体积可达1.794 cm^(3)g^(-1),能够均匀包封65%硒。此外,硒与碳之间的强化学键有利于稳定硒,从而进一步缓解其巨大的体积膨胀和多硒化物的溶解,还可促进循环过程中的电荷转移。该HPC@Se正极呈现出极好的循环性能和倍率性能。在0.2 C的电流密度下,经200次循环后,其比容量可保持在561 m Ahg^(-1)(为理论比容量的83%),每次循环的比容量衰减率仅为0.058%。此外,在5 C的高电流密度下,HPC@Se正极还可以达到472.8 m Ahg^(-1)的可观容量。
基金financially supported by the National Natural Science Foundation of China(Nos.21373195 and 51622210)the Fundamental Research Funds for the Central Universities(No.WK3430000004)
文摘Li–S and Li–Se batteries have attracted tremendous attention during the past several decades, as the energy density of Li–S and Li–Se batteries is high（several times higher than that of traditional Li-ion batteries）.Besides, Li–S and Li–Se batteries are low cost and environmental benign. However, the commercial applications of Li–S and Li–Se batteries are hindered by the dissolution and shuttle phenomena of polysulfide（polyselenium）, the low conductivity of S（Se）, etc. To overcome these drawbacks, scientists have come up with various methods, such as optimizing the electrolyte, synthesizing composite electrode of S/polymer, S/carbon, S/metal organic framework（MOF） and constructing novelty structure of battery.In this review, we present a systematic introduction about the recent progress of Li–S and Li–Se batteries, especially in the area of electrode materials, both of cathode material and anode material for Li–S and Li–Se batteries. In addition, other methods to lead a high-performance Li–S and Li–Se batteries are also briefly summarized, such as constructing novelty battery structure, adopting proper charge–discharge conditions, heteroatom doping into sulfur molecules, using different kinds of electrolytes and binders. In the end of the review, the developed directions of Li–S and Li–Se batteries are also pointed out. We believe that combining proper porous carbon matrix and heteroatom doping may further improve the electrochemical performance of Li–S and Li–Se batteries. We also believe that Li–S and Li–Se batteries will get more exciting results and have promising future by the effort of battery community.
基金financially supported by the National Basic Research Program of China(No.2014CB932400)the National Science Foundation of China(Nos.21406161 and 51602220)
文摘A dual functional CNTs@graphene/CNTs cathode for Li–Se battery was constructed by a CNTs@graphene network and a CNTs interlayer. CNTs were first integrated with graphene to form a three-dimensional（3D） framework and work together as a conductive matrix for Se confinement. The optimized composite cathode delivers a high initial capacity of 575 mAh·g^-1 at 0.5 A·g^-1 and good rate capacity with a retained capacity of 479 mAh·g^-1 at 2.0 A·g^-1（73% of the capacity at 0.2 A·g^-1）. CNTs were further served as an interlayer to confine the diffusion of polyselenides by constructing a thin CNTs layer outside the CNTs@graphene network. An improved initial capacity of 616 mAh·g^-1 at 0.5 A·g^-1 is achieved with a retained capacity of 538 mAh·g^-1 after 80 cycles, indicating the effective dual function of CNTs in this novel cathode construction and great application potential for Li–Se battery.
基金financially supported by the National Natural Science Foundation of China(Nos.51272156,21373137 and 21333007)the City Committee of Science and Technology Project of Shanghai(No.14JC1491800)the New Century Excellent Talents in University(Nos.NCET-13-0371)
文摘Animal bone was employed as raw material to prepare hierarchical porous carbon by KOH activation. Rare metal selenium（Se） was encapsulated into hierarchical porous carbon successfully for the cathode material of Li–Se battery, achieving the transformation of waste into energy,protecting environment and reducing the spread of the disease. Animal bone porous carbon（ABPC） acquires a specific surface area of 1244.7903 m^2·g^-1 and a pore volume of 0.594184 cm^3·g^-1. The composite Se/ABPC with 51 wt%Se was tested as a novel cathode for Li–Se batteries. The results show that Se/ABPC exhibits high specific capacity,good cycling stability and current-rate performance; at 0.1C,the composite Se/ABPC delivers a high reversible capacity of 705 mAh·g^-1 in the second cycle and 591 mAh·g^-1 after 98 cycles. Even at the current density of 2.0C, it can still maintain at a reversible capacity of 485 mAh·g^-1. The excellent electrochemical properties benefit from the high electron conductivity and the carbon with unique hierarchical porous structure. ABPC can be a promising carbon matrix for Li–Se batteries.
