Flexible and Binder‐Free Electrodes of Sb/rGO and Na3V2(PO4)3/rGO Nanocomposites for Sodium‐Ion Batteries

Flexible power sources have shown great promise in next‐generation bendable, implantable, and wearable electronic systems. Here, flexible and binder‐free electrodes of Na₃V₂(PO₄)₃/reduced graphene oxide (NVP/rGO) and Sb/rGO nanocomposites for sodium‐ion batteries are reported. The Sb/rGO and NVP/rGO paper electrodes with high flexibility and tailorability can be easily fabricated. Sb and NVP nanoparticles are embedded homogenously in the interconnected framework of rGO nanosheets, which provides structurally stable hosts for Na‐ion intercalation and deintercalation. The NVP/rGO paper‐like cathode delivers a reversible capacity of 113 mAh g^?1 at 100 mA g^?1 and high capacity retention of ≈96.6% after 120 cycles. The Sb/rGO paper‐like anode gives a highly reversible capacity of 612 mAh g^?1 at 100 mA g^?1, an excellent rate capacity up to 30 C, and a good cycle performance. Moreover, the sodium‐ion full cell of NVP/rGO//Sb/rGO has been fabricated, delivering a highly reversible capacity of ≈400 mAh g^?1 at a current density of 100 mA g^?1 after 100 charge/discharge cycles. This work may provide promising electrode candidates for developing next‐generation energy‐storage devices with high capacity and long cycle life.     

新型锂离子电池负极材料COFe3Sb12

用高能球磨方法制备出CoFe3Sb12合金粉末,研究了电化学性能。结果表明,CoFe3Sb12中的活性元素Sb可以与锂离子发生可逆电化学反应,其嵌锂产物为Li3Sb。CoFe3Sb12电极在20mA/g的电流密度下第一次可逆容量为396mAh/g。在材料中加入原子分数为50％的石墨（化学计量式为CoFe3Sb12-C16)后,以100mA/g进行充放电时,第一次可逆容量为380mAh/g。电极的循环寿命性能优良。     

In-situ encapsulation of α-Fe2O3 nanoparticles into ZnFe2O4 micro-sized capsules as high-performance lithium-ion battery anodes

Transition metal oxides as anode materials for high-performance lithium-ion batteries suffer from severe capacity decay,originating primarily from particle pulverization upon volume expansion/shrinkage and the intrinsically sluggish electron/ion transport.Herein,in-situ encapsulation of α-Fe2O3 nanoparticles into micro-sized ZnFe2O4 capsules is facilely fulfilled through a co-precipitation process and followed by heat-treatment at optimal calcination temperature.The porous ZnFe2C4 scaffold affords a synergistic confinement effect to suppress the grain growth of α-Fe2O3 nanocrystals during the calcination process and to accommodate the stress generated by volume expansion during the charge/discharge process,leading to an enhanced interfacial conductivity and inhibit electrode pulverization and mechanical failure in the active material.With these merits,the prepared α-Fe2O3/ZnFe2O4 composite delivers prolonged cycling stability and improved rate capability with a higher specific capacity than sole α-Fe2O3 and ZnFe2O4.The discharge capacity is retained at 700 mAh g-1 after 500 cycles at 200 mA g-1 and 940 mAh g-1 after 50 cycles at 100 mA g-1.This work provides a new perspective in designing transition metal oxides for advanced lithium-ion batteries with superior electrochemical properties.     

Understanding of the capacity contribution of carbon in phosphorus-carbon composites for high-performance anodes in lithium ion batteries

Phosphorus has recently received extensive attention as a promising anode for lithium ion batteries (LIBs) due to its high theoretical capacity of 2,596 mAh·g-1.To develop high-performance phosphorus anodes for LIBs,carbon materials have been hybridized with phosphorus (P-C) to improve dispersion and conductivity.However,the specific capacity,rate capability,and cycling stability of P-C anodes are still less than satisfactory for practical applications.Furthermore,the exact effects of the carbon support on the electrochemical performance of the P-C anodes are not fully understood.Herein,a series of xP-yC anode materials for LIBs were prepared by a simple and efficient ball-milling method.6P-4C and 3P-7C were found to be optimum mass ratios of x/y,and delivered initial discharge capacities of 1,803.5 and 1,585.3.mAh.g-1,respectively,at 0.1 C in the voltage range 0.02-2 V,with an initial capacity retention of 68.3％ over 200 cycles (more than 4 months cycling life) and 40.8％ over 450 cycles.The excellent electrochemical performance of the 6P-4C and 3P-7C samples was attributed to a synergistic effect from both the adsorbed P and carbon.     

Interface-modulated fabrication of hierarchical yolk–shell Co<Subscript>3</Subscript>O<Subscript>4</Subscript>/C dodecahedrons as stable anodes for lithium and sodium storage

Transition-metal oxides (TMOs) have gradually attracted attention from researchers as anode materials for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) because of their high theoretical capacity.However,their poor cycling stability and inferior rate capability resulting from the large volume variation during the lithiation/sodiation process and their low intrinsic electronic conductivity limit their applications.To solve the problems of TMOs,carbon-based metal-oxide composites with complex structures derived from metal-organic frameworks (MOFs) have emerged as promising electrode materials for LIBs and SIBs.In this study,we adopted a facile interface-modulated method to synthesize yolk-shell carbon-based Co3O4 dodecahedrons derived from ZIF-67 zeolitic imidazolate frameworks.This strategy is based on the interface separation between the ZIF-67 core and the carbon-based shell during the pyrolysis process.The unique yolk-shell structure effectively accommodates the volume expansion during lithiation or sodiation,and the carbon matrix improves the electrical conductivity of the electrode.As an anode for LIBs,the yolk-shell Co3O4/C dodecahedrons exhibit a high specific capacity and excellent cycling stability (1,100 mAh·g-1 after 120 cycles at 200 mA·g-1).As an anode for SIBs,the composites exhibit an outstanding rate capability (307 mAh·g-1 at 1,000 mA·g-1 and 269 mAh·g-1 at 2,000 mA·g-1).Detailed electrochemical kinetic analysis indicates that the energy storage for Li+ and Na+ in yolk-shell Co3O4/C dodecahedrons shows a dominant capacitive behavior.This work introduces an effective approach for fabricating carbonbased metal-oxide composites by using MOFs as ideal precursors and as electrode materials to enhance the electrochemical performance of LIBs and SIBs.     

Ultrafine Sn nanocrystals in a hierarchically porous N-doped carbon for lithium ion batteries

We report a simple method of preparing a high performance,Sn-based anode material for lithium ion batteries (LIBs).Adding H2O2 to an aqueous solution containing Sn2+ and aniline results in simultaneous polymerization of aniline and oxidation of Sn2+ to SnO2,leading to a homogeneous composite of polyaniline and SnO2.Hydrogen thermal reduction of the above composite yields N-doped carbon with hierarchical porosity and homogeneously distributed,ultrafine Sn particles.The nanocomposite exhibits excellent performance as an anode material for lithium ion batteries,showing a high reversible specific capacity of 788 mAh·g-1 at a current density of 100 mA·g-1 after 300 cycles and very good stability up to 5,000 mA·g-1.The simple preparation method combined with the good electrochemical performance is highly promising to promote the application of Sn based anode materials.     

基于Fe/Co-MOF制备的高性能镍铁电池铁电极及其电化学性能

铁电极是构筑高性能镍铁电池的关键。本文报道了一种基于Fe/Co-MOF制备镍铁电池铁电极的新思路,并系统研究了该材料的电化学性能。XRD、SEM和HRTEM等结果表明,Fe/Co-MOF烧结产物以八面体颗粒为主,主要由Fe_3O_4相及少量Fe-Co合金构成。作为镍铁电池的阳极时,相比于未加入Co的材料,目标材料的电化学性能得到了明显改善。Fe/Co-MOF烧结产物的放电平台稳定在1.18V,比Fe-MOF烧结产物的放电平台(1.10V)高约0.08V。尽管Fe/Co-MOF烧结产物在前10次循环出现了明显的容量衰减,但之后保持了较好的循环稳定性能,在1.0A·g-1电流密度下循环90次后比容量稳定在233.1mAh·g-1,而Fe-MOF烧结后产物的比容量仅为181.2mAh·g-1。交流阻抗结果显示Fe/Co-MOF烧结产物表现出更低的电荷传递阻抗。     

Ultrahigh Rate Performance of Hollow Antimony Nanoparticles Impregnated in Open Carbon Boxes for Sodium‐Ion Battery under Elevated Temperature

Antimony is a competitive and promising anode material for sodium‐ion batteries (SIBs) due to its high theoretical capacity. However, the poor rate capability and fast capacity fading greatly restrict its practical application. To address the above issues, a facile and eco‐friendly sacrificial template method is developed to synthesize hollow Sb nanoparticles impregnated in open carbon boxes (Sb HPs@OCB). The as‐obtained Sb HPs@OCB composite exhibits excellent sodium storage properties even when operated at an elevated temperature of 50 °C, delivering a robust rate capability of 345 mAh g^?1 at 16 A g^?1 and rendering an outstanding reversible capacity of 187 mAh g^?1 at a high rate of 10 A g^?1 after 300 cycles. Such superior electrochemical performance of the Sb HPs@OCB can be attributed to the comprehensive characteristics of improved kinetics derived from hollow Sb nanoparticles impregnated into 2D carbon nanowalls, the existence of robust Sb? O? C bond, and enhanced pseudocapacitive behavior. All those factors enable Sb HPs@OCB great potential and distinct merit for large‐scale energy storage of SIBs.     

Electrochemical Intercalation of Sodium into Silicon Thin Film

In order to investigate the possibility of Si thin film as an anode for Na battery, we studied the electrochemical intercalation of sodium into the Si film. Amorphous Si thin film electrode was prepared using DC magnetron sputtering. Sodium ion could intercalate into Si thin film upto Na0.52Si, i.e. 530mAh · g-1-Si. The first discharge capacity was 80mAh.·g-1-Si, which meant reversible amount of sodium intercalation. The discharge capacity slightly decreased to 70mAh · g-1-Si after 10 cycles.     

Spinel-layered integrate structured nanorods with both high capacity and superior high-rate capability as cathode material for lithium-ion batteries

Spinel phase LiMn2O4 was successfully embedded into monoclinic phase layeredstructured Li2MrnO3 nanorods,and these spinel-layered integrate structured nanorods showed both high capacities and superior high-rate capabilities as cathode material for lithium-ion batteries (LIBs).Pristine Li2MnO3 nanorods were synthesized by a simple rheological phase method using α-MnO2 nanowires as precursors.The spinel-layered integrate structured nanorods were fabricated by a facile partial reduction reaction using stearic acid as the reductant.Both structural characterizations and electrochemical properties of the integrate structured nanorods verified that LiMn2O4 nanodomains were embedded inside the pristine Li2MnO3 nanorods.When used as cathode materials for LIBs,the spinel-layered integrate structured Li2MnO3 nanorods (SL-Li2MnO3) showed much better performances than the pristine layered-structured Li2MnO3 nanorods (L-Li2MnO3).When charge-discharged at 20 mA·g-1 in a voltage window of 2.0-4.8 V,the SL-Li2MnO3 showed discharge capadties of 272.3 and 228.4 mAh.g-1 in the first and the 60th cycles,respectively,with capacity retention of 83.8％.The SL-Li2MnO3 also showed superior high-rate performances.When cycled at rates of 1 C,2 C,5 C,and 10 C (1 C =200 mA·g-1) for hundreds of cycles,the discharge capacities of the SL-Li2MnO3 reached 218.9,200.5,147.1,and 123.9 mAh·g-1,respectively.The superior performances of the SL-Li2MnO3 are ascribed to the spineMayered integrated structures.With large capacities and superior high-rate performances,these spinel-layered integrate structured materials are good candidates for cathodes of next-generation high-power LIBs.     

PVDF-HFP基凝胶电解质用于LiNi0.5Co0.2Mn0.3O2三元正极锂离子电池

以聚偏氟乙烯-六氟丙烯(Poly(vinylidene fluoride-hexafluoropropylene),PVDF-HFP)为聚合物基体,新戊二醇二丙烯酸酯(Neopentyl glycol diacrylate,NPGDA)为交联剂,在引发剂偶氮二异丁腈(2,2′-Azobis(2-methylpropionitrile),AIBN)的作用下通过室温现场聚合法制备凝胶电解质用于锂离子电池。探索不同质量比PVDF-HFP/NPGDA对凝胶电解质性能和LiNi_(0.5)-Co_(0.2)Mn_(0.3)O_2三元正极锂离子电池性能的影响。结果表明,当质量比为1∶1时,凝胶电解质具有较高的离子电导率,为8.45mS·cm~(-1),锂离子迁移数为0.78,电化学窗口为4.5V。在电流密度30mA·g~(-1)恒流充放电,首次放电比容量为143mAh·g~(-1),循环50次后仍高达135.3mAh·g~(-1)。电流密度为300mA·g~(-1)时,放电比容量为100.2mAh·g~(-1)。     

真空蒸镀法制备Sb膜电极及其性能

采用真空蒸镀法制备了金属Sb膜电极, 通过XRD、SEM、恒流充放电循环、循环伏安(CV)等方法, 研究了Sb膜电极的结构、形貌和电化学性能, 并对嵌脱锂机理进行了分析. 结果表明: 蒸镀后, 金属Sb为六方晶体, (003)晶面择优取向. Sb膜电极与基底铜箔的微观形貌接近, Sb金属以片层颗粒堆积在Cu箔颗粒上面. 在首次嵌锂过程中, 能观察到Li₃Sb合金的生成和Sb相的消失, 在脱锂之后, 能观察到Sb相的重新出现和Li₃Sb合金的消失, 且Sb相还是回复到(003)面择优相. Sb膜电极的首次充放电比容量分别为652和454 mAh/g, 循环16周后放电比容量还为300 mAh/g, 性能远优于Sb粉电极.     

A High‐Capacity O2‐Type Li‐Rich Cathode Material with a Single‐Layer Li2MnO3 Superstructure

A high capacity cathode is the key to the realization of high‐energy‐density lithium‐ion batteries. The anionic oxygen redox induced by activation of the Li₂MnO₃ domain has previously afforded an O3‐type layered Li‐rich material used as the cathode for lithium‐ion batteries with a notably high capacity of 250–300 mAh g^?1. However, its practical application in lithium‐ion batteries has been limited due to electrodes made from this material suffering severe voltage fading and capacity decay during cycling. Here, it is shown that an O2‐type Li‐rich material with a single‐layer Li₂MnO₃ superstructure can deliver an extraordinary reversible capacity of 400 mAh g^?1 (energy density: ≈1360 Wh kg^?1). The activation of a single‐layer Li₂MnO₃ enables stable anionic oxygen redox reactions and leads to a highly reversible charge–discharge cycle. Understanding the high performance will further the development of high‐capacity cathode materials that utilize anionic oxygen redox processes.     

Boosting High-Rate Zinc-Storage Performance by the Rational Design of Mn2O3 Nanoporous Architecture Cathode

Manganese oxides are regarded as one of the most promising cathode materials in rechargeable aqueous Zn-ion batteries(ZIBs)because of the low price and high security.However,the practical application of Mn2O3 in ZIBs is still plagued by the low specific capacity and poor rate capability.Herein,highly crystalline Mn2O3 materials with interconnected mesostructures and controllable pore sizes are obtained via a ligand-assisted self-assembly process and used as high-performance electrode materials for reversible aqueous ZIBs.The coordination degree between Mn2+and citric acid ligand plays a crucial role in the formation of the mesostructure,and the pore sizes can be easily tuned from 3.2 to 7.3 nm.Ascribed to the unique feature of nanoporous architectures,excellent zinc-storage performance can be achieved in ZIBs during charge/discharge processes.The Mn2O3 electrode exhibits high reversible capacity(233 mAh g−1 at 0.3 A g−1),superior rate capability(162 mAh g−1 retains at 3.08 A g−1)and remarkable cycling durability over 3000 cycles at a high current rate of 3.08 A g−1.Moreover,the corresponding electrode reaction mechanism is studied in depth according to a series of analytical methods.These results suggest that rational design of the nanoporous architecture for electrode materials can effectively improve the battery performance.     

High lithium storage performance of Ni0.5Fe0.5O1−xNx thin film with NiO-type crystal structure

The large voltage hysteresis of the NiO anode, which owes much to the intermediate product Li₂NiO₂, is one of the main obstacles to its practical application in lithium-ion batteries. In this work, we show that the incorporation of Fe- and N-ions in the NiO lattice can suppress the formation of intermediate product Li₂NiO₂ and thus greatly reduces the voltage hysteresis of the NiO anode from ~1.2 to ~0.9 V. In comparison with the pure NiO electrode, the Ni_0.5Fe_0.5O_1−xN_x anode exhibits significantly enhanced reversible specific capacity (959 mAh·g⁻¹ at 0.3 A·g⁻¹), cycling stability (capacity retention of 96.1% at 100th cycle relative to the second cycle) and rate capability (442 at 10 A·g⁻¹). These results provide a practical method to enhance the lithium storage performance of the NiO anode and more importantly a new solution to the large voltage hysteresis of conversion-type anodes.     

新型嵌锂材料——锌锑合金

阐述了新型嵌锂材料锌锑合金的嵌锂特性及其嵌锂机理。将Ｚｎ４ Ｓｂ３ 球磨后得到ＺｎＳｂ 与ＺｎＯ复合相。用此复合相单独作电极得到２７２ｍ Ａｈ／ｇ 的容量,加入铜粉后可得到４６２ｍ Ａｈ／ｇ 的容量,可逆性提高。加入Ｌｉ２Ｏ不能提高可逆性。     

锂离子电池正极材料铁掺杂V_6O_(13)的制备及电化学性能

为有效提高V_6O_(13)正极材料在高锂状态下的放电比容量和改善循环性能,使用一种先制备前驱体再水热合成的方法制备铁掺杂V_6O_(13)。运用XRD,SEM和XPS表征铁掺杂V_6O_(13)的物相、形貌以及表面元素价态,并对铁掺杂V_6O_(13)的电化学性能进行研究与分析。掺杂不同数量的铁可以得到不同形貌且电化学性能各异的铁掺杂V_6O_(13)。其中0.02样品的有序堆垛纳米片的厚度最大(600~900nm),纳米片之间的空隙最大。铁掺杂V_6O_(13)样品的放电性能均好于纯V_6O_(13),其中0.02样品的电化学性能最好,首次放电比容量为433mAh·g-1,100次循环后的容量保存率为47.1%。     

An Advanced MoS2/Carbon Anode for High‐Performance Sodium‐Ion Batteries

Molybdenum disulfide (MoS₂) is a promising anode for high performance sodium‐ion batteries due to high specific capacity, abundance, and low cost. However, poor cycling stability, low rate capability and unclear electrochemical reaction mechanism are the main challenges for MoS₂ anode in Na‐ion batteries. In this study, molybdenum disulfide/carbon (MoS₂/C) nanospheres are fabricated and used for Na‐ion battery anodes. MoS₂/C nanospheres deliver a reversible capacity of 520 mAh g^?1 at 0.1 C and maintain at 400 mAh g^?1 for 300 cycles at a high current density of 1 C, demonstrating the best cycling performance of MoS₂ for Na‐ion batteries to date. The high capacity is attributed to the short ion and electron diffusion pathway, which enables fast charge transfer and low concentration polarization. The stable cycling performance and high coulombic efficiency (～100%) of MoS₂/C nanospheres are ascribed to (1) highly reversible conversion reaction of MoS₂ during sodiation/desodiation as evidenced by ex‐situ X‐ray diffraction (XRD) and (2) the formation of a stable solid electrolyte interface (SEI) layer in fluoroethylene carbonate (FEC) based electrolyte as demonstrated by fourier transform infrared spectroscopy (FTIR) measurements.     

Graphene‐Protected 3D Sb‐based Anodes Fabricated via Electrostatic Assembly and Confinement Replacement for Enhanced Lithium and Sodium Storage

Alloy anodes have shown great potential for next‐generation lithium‐ion batteries (LIBs) and sodium‐ion batteries (SIBs). However, these applications are still limited by inherent huge volume changes and sluggish kinetics. To overcome such limitations, graphene‐protected 3D Sb‐based anodes grown on conductive substrate are designed and fabricated by a facile electrostatic‐assembling and subsequent confinement replacement strategy. As binder‐free anodes for LIBs, the obtained electrode exhibits reversible capacities of 442 mAh g⁻¹ at 100 mA g⁻¹ and 295 mAh g⁻¹ at 1000 mA g⁻¹, and a capacity retention of above 90% (based on the 10th cycle) after 200 cycles at 500 mA g⁻¹. As for sodium storage properties, the reversible capacities of 517 mAh g⁻¹ at 50 mA g⁻¹ and 315 mAh g⁻¹ at 1000 mA g⁻¹, the capacity retention of 305 mAh g⁻¹ after 100 cycles at 300 mA g⁻¹ are obtained, respectively. Furthermore, the 3D architecture retains good structural integrity after cycling, confirming that the introduction of high‐stretchy and robust graphene layers can effectively buffer alloying anodes, and simultaneously provide sustainable contact and protection of the active materials. Such findings show its great potential as superior binder‐free anodes for LIBs and SIBs.     

MSb2型金属间化合物作为锂离子电池负极材料的研究

采用真空悬浮熔炼与高能球磨制备了MSb2(M＝Co和Fe)型合金粉末,利用恒电流电池测试仪研究了其电化学性能。研究发现CoSb2和FeSb2电极的嵌/脱锂平台均在0.8和1.0V左右;在20mA/g电流密度下的首次嵌锂反应的可逆容量为430mAh/g;电流密度为100mA/g条件下,CoSb2首次嵌锂反应的可逆容量为380mAh/g,FeSb2首次嵌锂反应的可逆容量340mAh/g。所以,MSb2型金属锑化物可以作为锂离子电池负极材料的侯选材料。,Sb-based inter-metallic compounds(MSb2) were prepared by levitation melting and milled by high-energy ball-mill.Experiments show that the plateaus of lithium ion insertion and extraction were at about 0.8 and 1.0V. Their reversible capacities are all about 430mAh/g and their cycle lives are almost same during the cycling at the current density of 20mA/g.But at the current density of 100mA/g they both have a little difference in the cycle life.The materials show the superior properties and can be considered as a candidater for the anode materials of lithium ion batteries.