FeS2@TiO2 nanorods as high-performance anode for sodium ion battery

Sodium-ion battery (SIB) is an ideal device that could replace lithium-ion battery (LIB) in grid-scale energy storage system for power because of the low cost and rich reserve of raw material. The key challenge lies in developing electrode materials enabling reversible Na⁺ insertion/desertion and fast reaction kinetics. Herein, a core-shell structure, FeS₂ nanoparticles encapsulated in biphase TiO₂ shell (FeS₂@TiO₂), is developed towards the improvement of sodium storage. The diphase TiO₂ coating supplies abundant anatase/rutile interface and oxygen vacancies which will enhance the charge transfer, and avoid severe volume variation of FeS₂ caused by the Na⁺ insertion. The FeS₂ core will deliver high theoretical capacity through its conversion reaction mechanism. Consequently, the FeS₂@TiO₂ nanorods display notable performance as anode for SIBs including long-term cycling performance (637.8 mA·h·g^-1 at 0.2 A·g^-1 after 300 cycles, 374.9 mA·h·g^-1 at 5.0 A·g^-1 after 600 cycles) and outstanding rate capability (222.2 mA·h·g^-1 at 10 A·g^-1). Furthermore, the synthesized FeS₂@TiO₂ demonstrates significant pseudocapacitive behavior which accounts for 90.7% of the Na⁺ storage, and efficiently boosts the rate capability. This work provides a new pathway to fabricate anode material with an optimized structure and crystal phase for SIBs.     

多级结构MoS2/C复合材料的储锂性能

利用二硫化钼和葡萄糖为原料,采用一锅乙醇/水复合溶剂热-后热处理法制备了绣球花状结构MoS₂/C复合材料。考查了乙醇/水复合溶剂的合理组成和MoS₂/C复合材料中碳的合理含量,分别采用SEM和TEM表征了MoS₂/C材料的形貌结构,通过TGA测试和计算了材料中的碳含量。采用循环伏安、恒流充放电和交流阻抗等测试了MoS₂/C复合电极的电化学性能。结果表明,MoS₂/C复合材料拥有多级花球状结构,缓解了MoS₂的团聚,使电极材料的利用率和电化学稳定性显著提高。当V（乙醇）：V（水）为1：2,碳含量为50%时,MoS₂/C复合电极在200 mA·g^-1的电流密度下,充放电循环100次后,可逆容量达到762 mA·h·g^-1。     

Pre-sodiation strategy for superior sodium storage batteries

The irreversible consumption of sodium in the initial several cycles greatly led to the attenuation of capacity, which caused the low initial coulombic efficiency (ICE) and obvious poor cycle stability. Pre-sodiation can effectively improve the electrochemical performance by compensating the capacity loss in the initial cycle. Here, carbon-coated sodium-pretreated iron disulfide (NaFeS₂@C) has been synthesized through conventional chemical method and used in sodium metal battery as a cathode material. The calculated density of states (DOS) of NaFeS₂@C is higher, which implies enhanced electron mobility and improved cycle reversibility. Because of the highly reversible conversion reaction and the compensation of irreversible capacity loss during the initial cycle, the Na/NaFeS₂@C battery achieves ultra-high initial coulombic efficiency (96.7%) and remarkable capacity (751 mA·h·g^-1 at 0.1 A·g^-1). In addition, highly reversible electrochemical reactions and ultra-thin NaF-rich solid electrolyte interphase (SEI) also benefit for the electrochemical performance, even at high current density of 100 A·g^-1, it still exhibits a reversible capacity of 136 mA·h·g^-1, and 343 mA·h·g^-1 after 2500 cycles at 5.0 A·g^-1. This work aims to bring up new insights to improve the ICE and stability of sodium metal batteries.     

Lithium Storage Performance of Hollow and Core/Shell TiO2 Microspheres Containing Carbon☆

TiO2 microspheres containing carbon have been synthesized viaa one-pot hydrothermal process using CTAB as the mesoporous template and nanoparticle stabilizer and Ti(SO4)2 and sucrose as titanium and ca...     

A facile preparation of 3D flower-shaped Ni/Al-LDHs covered by β-Ni(OH)2 nanoplates as superior material for high power application

In the present study, we propose a novel electrode material of β-nickel hydroxide covering nickel/aluminum layered double hydroxides via a facile complexation-precipitation method. The as-obtained materials with 3-dimensional nanostructures are further utilized as highly capable electrode material in nickel-metal hydride batteries. The electrochemical test results demonstrated the β-nickel hydroxide covering nickel/aluminum-layered double hydroxides with 28% of β-nickel hydroxide provided a superior specific capacity value of 452 mA·h·g^-1 in a current density of 5 A·g^-1 using 6 M KOH as electrolyte as compared with other materials. In addition, the optimized sample displays an outstanding cyclic stability along with a huge specific capacity value of 320 mAh·g^-1, and very small decay rate of 3.3% at 50 A·g^-1 after 3000 cycles of charge/discharge test. These indicate that the newly designed material with nanostructures not only provides an efficient contact interface between electrolyte and active species and facilitates the transport of electrons and ions, but also protects the 3-dimensional nickel/aluminum layered double hydroxides, achieving a high specific capacity, fast redox reaction and excellent long-term cyclic stability. Therefore, the β-nickel hydroxide covering nickel/aluminum layered double hydroxides with superior electrochemical performance is predictable to be a gifted electrode material in nickel-metal hydride batteries.     

秸秆基碳材料在Li2SO4电解液中的电化学性能

以生物质秸秆为碳源,利用水热结合KOH活化法制备了多孔碳材料,对其结构与形貌进行了表征。采用三电极体系,在不同浓度的Li₂SO₄电解液中,对多孔碳电极进行循环伏安、恒电流充放电和交流阻抗测试。结果表明,在0.5 mol·L^-1的Li₂SO₄电解液中,秸秆基生物质碳材料呈现出较好的电化学性能。当电流密度为0.5 A·g^-1时,比电容可达224 F·g^-1;经1500次充放电测试后,比电容保持率高达94.1%,循环性能良好。     

Effective enhancement of the electrochemical properties for Na2FeP2O7/C cathode materials by boron doping

In recent years, the composite materials based on polyanionic frameworks as secondary sodium ion battery electrode material have been developed in large-scale energy storage applications due to its safety and stability. The Na₂FeP₂O₇/C (theoretical capacity 97 mA·h·g^-1) is recognized as optimum Na-storage cathode materials with a trade-off between electrode performance and cost. In the present work, The Na₂FeP₂O₇/C and boron-doped Na₂FeP_2-BO₇/C composites were synthesized via a novel method of liquid phase combined with high temperature solid phase. The non-metallic element B doping not only had positive influence on the crystal structure stability, Na⁺ diffusion and electrical conductivity of Na₂FeP₂O₇/C, but also contributed to the high-value recycling of B element in waste borax. The structure and electrochemical properties of the cathode material were investigated via X-ray diffraction (XRD), scanning electron microscopy (SEM), The X-ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and charge/discharge cycling. The results showed that different amounts of boron doping had positive effects on the structure and electrochemical properties of the material. The initial charge/discharge performances of born doped materials were improved in comparison to the bare Na₂FeP₂O₇/C. The cycle performance of the Na₂FeP_1.95B_0.05O₇/C showed an initial reversible capacity of 74.8 mA·h·g^-1 and the high capacity retention of 91.8% after 100 cycles at 1.0 C, while the initial reversible capacity of the bare Na₂FeP₂O₇/C was only 66.2 mA·h·g^-1. The improvement of apparent Na⁺ diffusion and electrical conductivity due to B doping were verified by the EIS test and CVs at various scan rate. The experimental results from present work is useful for opening new insight into the contrivance and creation of applicable sodium polyanionic cathode materials for high-performance.     

二硫化钼纳米片基水处理纳滤/反渗透膜研究进展

二硫化钼（MoS₂）纳米片的层内固有缺陷以及层间纳米限域通道的存在,有利于提高水处理纳滤/反渗透（NF/RO）膜的渗透选择性。本文首先介绍了MoS₂纳米片的“三明治”结构,其具有易功能化、高吸附容量和氧化还原去除能力、层间纳米限域通道的光滑性和稳定性及抗污染等特性;然后重点综述了MoS₂基纳米孔膜、层叠膜和混合基质膜的制备方法及膜性能的影响因素;最后总结了MoS₂纳米片基水处理NF/RO膜未来发展亟待解决的关键问题,主要包括研究大尺寸纳米片和均匀亚纳米孔的可控制备方法,开发超薄、高度有序的MoS₂分离层构建方法,探索层间纳米限域通道内分子和离子的传输行为和潜在的分离机理,开发增强与聚合物基质界面相容性的改性策略,对下一代高性能水处理NF/RO膜的研发具有启发意义。     

锂离子电池负极材料Li4Ti5O12/C的制备与表征

针对Li₄Ti₅O₁₂导电性和倍率性能差的缺陷,以PEG为碳源采用溶胶-凝胶法制备出电池负极材料Li₄Ti₅O₁₂/C,考察不同分子量聚乙二醇PEG(400、600、1000)做碳源制备的Li₄Ti₅O₁₂/C复合材料电化学性能的优劣,采用热重分析仪(TG)、X射线衍射仪(XRD)、扫描电镜(SEM)、透射电镜(TEM)、恒流充放电、倍率放电、交流阻抗(EIS)等方法对材料进行了结构表征和电化学性能测试。结果表明:以PEG1000为碳源时得到的Li₄Ti₅O₁₂/C,0.1C下首次放电比容量为143.5 mA·h·g^-1,2C的倍率下仍然保持了105 mA·h·g^-1的比容量,容量保持率达到73.17%,并且此材料有最小的电阻,在大电流条件下有良好的电化学性能。     

Three-dimensional oxygen-doped porous graphene: Sodium chloride-template preparation,structural characterization and supercapacitor performances

Supercapacitor is a new type of energy storage device, which has the advantages of high-power property and long cycle life. In this study, three-dimensional graphene (3D-GN) with oxygen doping and porous structure was prepared from graphene oxide (GO) by an inexpensive sodium chloride (NaCl) template, as a promising electrode material for the supercapacitor. The structure, morphology, specific surface area, pore size, of the sample were characterized by XRD, SEM, TEM and BET techniques. The electrochemical performances of the sample were tested by CV and CDC techniques. The 3D-GE product is a three-dimensional nano material with hierarchical porous structures, its specific surface area is much larger than that of routine stacked graphene (GN), and it contains a large number of mesoporous and macropores, a small amount of micropores. The capacitance characteristics of the 3D-GN electrode material are excellent, showing high specific capacitance (173.5 F·g^-1 at 1 A·g^-1), good rate performance (109.2 F·g^-1 at 8 A·g^-1) and long cycle life (88% capacitance retention after 10,000 cycles at 8 A·g^-1)     

Facile synthesis of spinel LiNi0.5Mn1.5O4 as 5.0 V-class high-voltage cathode materials for Li-ion batteries

LiNi_0.5Mn_1.5O₄ and LiMn₂O₄ with novel spinel morphology were synthesized by a hydrothermal and post-calcination process. The synthesized LiMn₂O₄ particles (5-10 μm) are uniform hexahedron, while the LiNi_0.5Mn_1.5O₄ has spindle-like morphology with the long axis 10-15 μm, short axis 5-8 μm. Both LiMn₂O₄ and LiNi_0.5Mn_1.5O₄ show high capacity when used as cathode materials for Li-ion batteries. In the voltage range of 2.5-5.5 V at room temperature, the LiNi_0.5Mn_1.5O₄ has a high discharge capacity of 135.04 mA·h·g^-1 at 20 mA·g^-1, which is close to 147 mA·h·g^-1 (theoretical capacity of LiNi_0.5Mn_1.5O₄). The discharge capacity of LiMn₂O₄ is 131.08 mA·h·g^-1 at 20 mA·g^-1. Moreover, the LiNi_0.5Mn_1.5O₄ shows a higher capacity retention (76%) compared to that of LiMn₂O₄ (61%) after 50 cycles. The morphology and structure of LiMn₂O₄ and LiNi_0.5Mn_1.5O₄ are well kept even after cycling as demonstrated by SEM and XRD on cycled LiMn₂O₄ and LiNi_0.5Mn_1.5O₄ electrodes.     

Spongy acetylenic carbon material prepared by ball milling CaC2 and chlorinated rubber — Its mercury adsorption and electrochemical property

Design and preparation of novel advanced carbon materials with unique architecture and functional groups is of great significance. Herein, a spongy acetylenic carbon material (SACM) was prepared through mechanochemical reaction of CaC₂ and chlorinated rubber in a planetary ball mill at ambient temperature. Its composition and structure were characterized, and its electrochemical properties and adsorption performance for Hg²⁺ were studied. The SACM is composed of submicron spongy aggregates with high carbon content (81.8%) and specific area (503.9 m²·g^-1), rich porosity and acetylenic groups. The SACM exhibits excellent adsorption for Hg²⁺ with saturated adsorption amount being 157.1 mg·g^-1, which is superior to conventional carbon materials. Further, it exhibits good electrochemical performance with low equivalent series resistance (0.50 Ω), excellent cycling stability and ideal double layer capacitive behavior. This paper provides a novel and universal synthesis method of spongy carbon materials, and better results can be expected through tuning the pore structure, graphitization degree, and heteroatoms of the target carbon materials.     

石墨烯/δ-MnO2复合材料的制备及其超级电容器性能

采用螯合法制备了RGO/δ-MnO₂复合材料,并用X射线粉末衍射（XRD）、低压氮气吸附脱附（BET）、X射线光电子能谱（XPS）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、能谱（EDS）、热重（TGA）对其结构和物相进行表征。采用循环伏安测试（CV）、恒电流充放电（GCD）以及循环测试对所制材料电化学储能进行测试。结果表明RGO/δ-MnO₂复合材料比纯石墨烯和纯δ-MnO₂具有更优异的电化学性能。当电流密度为1 A·g^-1时,RGO/δ-MnO₂复合材料的比电容可达322.6 F·g^-1,比纯δ-MnO₂电极材料高234.2 F·g^-1,比纯石墨烯高212.1 F·g^-1。当电流密度放大10倍后,RGO/δ-MnO₂复合材料的比电容保留率为79.1%。在1000次恒流充放电测试后,比电容为252 F·g^-1（99.6%）,说明该方法制备的RGO/δ-MnO₂复合材料是一种有应用前景的超级电容器电极材料。     

响应面法优化碳热还原合成LiFePO4/C的工艺参数（英文）

A statistically based optimization strategy is used to optimize the carbothermal reduction technology for the synthesis of LiFePO4/C using LiOH,FePO4 and sucrose as raw materials.The experimental data for fitting the response are collected by the central composite rotatable design(CCD).A second order model for the discharge ca-pacity of LiFePO4/C is expressed as a function of sintering temperature,sintering time and carbon content.The ef-fects of individual variables and their interactions are studied by a statistical analysis(ANOVA).The results show that the linear effects and the quadratic effects of sintering temperature,carbon content and the interactions among these variables are statistically significant,while those effects of sintering time are insignificant.Response surface plots for spatial representation of the model illustrate that the discharge capacity depends on sintering temperature and carbon content more than sintering time.The model obtained gives the optimized reaction parameters of sinter-ing temperature at 652.0 ℃,carbon content of 34.33 g?mol-1 and 8.48 h sintering time,corresponding to a dis-charge capacity of 150.8 mA·h·g-1.The confirmatory test with these optimum parameters gives the discharge ca-pacity of 147.2 and 105.1 mA·h·g-1 at 0.5 and 5 C,respectively.     

Synthesis of Chl@Ti3C2 composites as an anode material for lithium storage

Two-dimensional (2D) titanium carbide MXene Ti₃C₂ has attracted significant research interest in energy storage applications. In this study, we prepared Chl@Ti₃C₂ composites by simply mixing a chlorophyll derivative (e.g., zinc methyl 3-devinyl-3-hydroxymethyl- pyropheophorbide a (Chl)) and Ti₃C₂ in tetrahydrofuran, where the Chl molecules were aggregated among the multi-layered Ti₃C₂ MXene or on its surface, increasing the interlayer space of Ti₃C₂. The as-prepared Chl@Ti₃C₂ was employed as the anode material in the lithium-ion battery (LIB) with lithium metal as the cathode. The resulting LIB exhibited a higher reversible capacity and longer cycle performance than those of LIB based on pure Ti₃C₂, and its specific discharge capacity continuously increased along with the increasing number of cycles, which can be attributed to the gradual activation of Chl@Ti₃C₂ accompanied by the electrochemical reactions. The discharge capacity of 1 wt-% Chl@Ti₃C₂ was recorded to be 325 mA·h·g^–1 at the current density of 50 mA·g^–1 with a Coulombic efficiency of 56% and a reversible discharge capacity of 173 mA·h·g^–1 at the current density of 500 mA·g^–1 after 800 cycles. This work provides a novel strategy for improving the energy storage performance of 2D MXene materials by expanding the layer distance with organic dye aggregates.     

Nitrogen-doped carbon stabilized LiFe0.5Mn0.5PO4/rGO cathode materials for high-power Li-ion batteries

Exploring high ion/electron conductive olivine-type transition metal phosphates is of vital significance to broaden their applicability in rapid-charging devices. Herein, we report an interface engineered LiFe_0.5Mn_0.5PO₄/rGO@C cathode material by the synergistic effects of rGO and polydopamine-derivedN-doped carbon. The well-distributed LiFe_0.5Mn_0.5PO₄ nanoparticles are tightly anchored on rGO nanosheet benefited by the coating of N-doped carbon layer. The design of such an architecture can effectively suppress the agglomeration of nanoparticles with a shortened Li⁺ transfer path. Meantime, the high-speed conducting network has been constructed by rGO and N-doped carbon, which exhibits the face-to-face contact with LiFe_0.5Mn_0.5PO₄ nanoparticles, guaranteeing the rapid electron transfer. These profits endow the LiFe_0.5Mn_0.5PO₄/rGO@C hybrids with a fast charge-discharge ability, e.g. a high reversible capacity of 105 mAh·g^-1 at 10 C, much higher than that of the LiFe_0.5Mn_0.5PO₄@C nanoparticles (46 mA·h·g^-1). Furthermore, a 90.8% capacity retention can be obtained even after cycling 500 times at 2 C. This work gives a new avenue to fabricate transition metal phosphate with superior electrochemical performance for high-powerLi-ion batteries.     

原位合成的介孔TiO2-B/锐钛微粒:改善的锂离子电池阳极材料（英文）

Mesoporous TiO2-B/anatase microparticles have been in-situ synthesized from K2Ti2O5 without template. The TiO2-B phase around the particle surface accelerates the diffusion of charges through the interface, while the anatase phase in the core maintains the capacity stability. The heterojunction interface between the main polymorph of anatase and the trace of TiO2-B exhibits promising lithium ion battery performance. This trace of 5%(by mass) TiO2-B determined by Raman spectra brings the first discharge capacity of this material to 247 mA·h·g?1, giving 20%improvement com-pared to the anatase counterpart. Stability testing at 1 C reveals that the capacity maintains at 171 mA·h·g?1, which is better than 162 mA·h·g?1 for single phase anatase or 159 mA·h·g?1 for TiO2-B. The mesoporous TiO2-B/anatase microparticles also show superior rate performance with 100 mA·h·g?1 at 40 C, increased by nearly 25%as compared to pure anatase. This opens a possibility of a general design route, which can be applied to other metal oxide electrode materials for rechargeable batteries and supercapacitors.     

高分散SiO2/石油沥青基多孔碳用于锂离子电池负极

二氧化硅(SiO₂)作为锂离子电池负极材料具有理论容量高、放电电位低、成本较低等特点,但存在导电性差、充放电过程体积膨胀严重以及容量衰减过快等问题。以石油沥青为碳源,利用硅烷偶联剂KH-540对纳米α-Fe₂O₃模板剂进行表面化学包覆,然后将硅源修饰模板剂与碳源混合,经碳化、酸洗等步骤得到高分散SiO₂/石油沥青基多孔碳(SiO₂/PC)。所得SiO₂/PC作为锂离子电池负极材料,在1 A·g^-1电流密度下,循环900圈后仍具有640 mA·h·g^-1的高可逆比容量。研究结果表明,高度纳米化的SiO₂在高温碳化过程原位生成,紧密牢固地负载于多孔碳表面,提高了其导电性,同时能够有效缓解SiO₂在充放电过程中的体积膨胀,抑制SiO₂的团聚或粉化,从而表现出优异的电化学性能。     

纳米b-Ni(OH)2的制备及其储锂性能

以Ni(NO₃)₂·6H₂O和NaOH为原料采用化学沉淀法制备了Ni(OH)₂电极材料。采用X射线衍射(XRD)和场发射扫描电子显微镜(FESEM)表征了样品的微观结构,结果表明该样品是具有片状纳米次级结构的β-Ni(OH)₂。采用循环伏安(CV)和电化学充放电测试研究了该β-Ni(OH)₂样品的储锂性能,结果发现该样品作为锂离子电池负极材料具有非常高的储锂活性,在50 mA·g^-1电流密度下其第3次循环放电比容量高于1550 mA·h·g^-1;样品电极中的碳含量对其循环性能和倍率性都有显著影响,通过交流阻抗(EIS)测试分析了样品电极中碳含量的作用机理。     

珊瑚状氮掺杂多孔碳的制备及其超电容性能

在三聚氰胺为氮源、碳酸钾为活化剂的条件下,由菜籽饼制得了珊瑚状氮掺杂分级多孔碳(CNPCs)。采用场发射扫描电子显微镜、透射电子显微镜、X射线光电子能谱、氮吸脱附等表征手段,研究了三聚氰胺的用量对CNPCs微观形貌、组成及孔隙结构的影响。结果表明,当三聚氰胺的用量为2 g时,所得CNPC₂的比表面积达2050 m²·g^-1。以6 mol·L^-1 KOH为电解液,在0.05 A·g^-1的电流密度下,CNPCs的比容可达274 F·g^-1;当电流密度为50 A·g^-1时,CNPCs的比容为169 F·g^-1,显示了优异的倍率性能。经过10000次充放电测试后,比容保持率达96%,展现了良好的循环稳定性。此工作为从生物质大规模生产高性能储能用多孔碳材料提供了一种简单、绿色的方法。