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.     

Si/C particles on graphene sheet as stable anode for lithium-ion batteries

Silicon is considered as one of the most promising anodes for Li-ion batteries (LIBs),but it is limited for commercial applications by the critical issue of large volume expansion during the lithiation.In this work,the structure of silicon/carbon (Si/C) particles on graphene sheets (Si/C-G) was obtained to solve the issue by using the void space of Si/C particles and graphene.Si/C-G material was from Si/PDA-GO that silicon particles was coated by polydopamine (PDA) and reacted with oxide graphene (GO).The Si/C-G material have good cycling performance as the stability of the structure during the lithiation/dislithiation.The Si/C-G anode materials exhibited high reversible capacity of 1910.5 mA h g-1 and 1196.1 mA h g-1 after 700 cycles at 357.9 mA g-1,and have good rate property of 507.2 mA h g-1 at high current density,showing significantly improved commercial viability of silicon electrodes in high-energy-density LIBs.     

Nanoscale Borate Coating Network Stabilized Iron Oxide Anode for High-Energy-Density Bipolar Lithium-Ion Batteries

High-capacity metal oxides based on non-toxic earth-abundant elements offer unique opportunities as advanced anodes for lithium-ion batteries (LIBs). But they often suffer from large volumetric expansion, particle pulverization, extensive side reactions, and fast degradations during cycling. Here, an easy synthesis method is reported to construct amorphous borate coating network, which stabilizes conversion-type iron oxide anode for the high-energy-density semi-solid-state bipolar LIBs. The nano-borate coated iron oxide anode has high tap density (1.6 g cm⁻³), high capacity (710 mAh g⁻¹ between 0.5 – 3.0 V, vs Li/Li⁺), good rate performance (200 mAh g⁻¹ at 50 C), and excellent cycling stability (≈100% capacity resention over 1,000 cycles at 5 A g⁻¹). When paired with high-voltage cathode LiCoO₂, it enables Cu current collector-free pouch-type classic and bipolar full cells with high voltage (7.6 V with two stack layers), achieving high energy density (≈350 Wh kg⁻¹), outstanding power density (≈6,700 W kg⁻¹), and extended cycle life (75% capacity retention after 2,000 cycles at 2 C), superior to the state-of-the-art high-power LIBs using Li₄Ti₅O₁₂ anode. The design and methodology of the nanoscale polyanion-like coating can be applied to other metal oxides electrode materials, as well as other electrochemical materials and devices.     

Micro-nano structured VNb9O25 anode with superior electronic conductivity for high-rate and long-life lithium storage

The oxygen vacancies and micro-nano structure can optimize the electron/Li+migration kinetics in anode materials for lithium batteries(LIBs).Here,porous micro-nano structured VNb9O25 composites with rich oxygen vacancies were reasonably prepared via a facile solvothermal method combined with annealing treatment at 800℃for 30 h(VNb9 O25-30 h).This micro-nano structure can enhance the contact of active material/electrolyte,and shorten the Li+diffusion distance.The introduction of oxygen vacancies can further boosts the intrinsic conductivity of VNb9O25-30 h for achieving excellent LIB performance.The as-prepared VNb9O25-30 h anode showed advanced rate capability with reversible capacity of 122.2 mA h g-1 at 4 A g-1,and delivered excellent capacity retention of～100％after 2000 cycles.Meanwhile,VNb9O25-30 h provides unexpected long-cycle life(i.e.,reversible capacity of 165.7 mA h g-1 at 1 A g-1 with a high capacity retention of 85.6％even after 8000 cycles).Additionally,coupled with the LiFePO4 cathode,the LiFePO4//VNb9O25-30 h full cell delivers superior LIB properties with high reversible capacities of 91.6 mA h g-1 at 5C for 1000 cycles.Thus,such reasonable construction method can assist in other high-performance niobium-based oxides in LIBs.     

Hollow multi-nanochannel carbon nanofiber/MoS2 nanoflower composites as binder-free lithium-ion battery anodes with high capacity and ultralong-cycle life at large current density

The electrode materials with high pseudocapacitance can enhance the rate capability and cycling stabil-ity of lithium-ion storage devices.Herein,we fabricated MoS2 nanoflowers with ultra-large interlayer spacing on N-doped hollow multi-nanochannel carbon nanofibers(F2-MoS2/NHMCFs)as freestanding binder-free anodes for lithium-ion batteries(LIBs).The ultra-large interlayer spacing(0.78～1.11 nm)of MoS2 nanoflowers can not only reduce the internal resistance,but also increase accessible active sur-face area,which ensures the fast Li+intercalation and deintercalation.The NHMCFs with hollow and multi-nanochannel structure can accommodate the large internal strain and volume change during lithi-ation/delithiation process,it is beneficial to improving the cycling stability of LIBs.Benefiting from the above combined structure merits,the F2-MoS2/NHMCFs electrodes deliver a high rate capability 832 mA h g-1 at 10 A g-1 and ultralong cycling stability with 99.29 and 91.60％capacity retention at 10 A g-1 after 1000 and 2000 cycles,respectively.It is one of the largest capacities and best cycling stability at 10 A g-1 ever reported to date,indicating the freestanding F2-MoS2/NHMCFs electrodes have potential applications in high power density LIBs.     

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.     

Nitrogen and Phosphorus Codoped Vertical Graphene/Carbon Cloth as a Binder‐Free Anode for Flexible Advanced Potassium Ion Full Batteries

With the fast development in flexible electronic technology, power supply devices with high performance, low‐cost, and flexibility are becoming more and more important. Potassium ion batteries (KIBs) have a brilliant prospect for applications benefiting from high voltage, lost cost, as well as similar electrochemistry to lithium ion batteries (LIBs). Although carbon materials have been studied as KIBs anodes, their rate capability and cycling stability are still unsatisfactory due to the large‐size potassium ions. Herein, a nitrogen (N) and phosphorus (P) dual‐doped vertical graphene (N, P‐VG) uniformly grown on carbon cloth (N, P‐VG@CC) is reported as a binder‐free anode for flexible KIBs. With the combined advantages of rich active sites, highly accessible surface, highly conductive network, larger interlayer spacing as well as robust structural stability, this binder‐free N, P‐VG@CC anode exhibits high capacity (344.3 mAh g^?1), excellent rate capability (2000 mA g^?1; 46.5% capacity retention), and prominent long‐term cycling stability (1000 cycles; 82% capacity retention), outperforming most of the recently reported carbonaceous anodes. Moreover, a potassium ion full cell is successfully assembled on the basis of potassium Prussian blue (KPB)//N, P‐VG@CC, exhibiting a large energy density of 232.5 Wh kg^?1 and outstanding cycle stability.     

ZnS-PANI nanocomposite with enhanced electrochemical performances for lithium-ion batteries

A simple two-step method of coprecipitation followed by polymerization successfully yielded ZnS-PANI nanocomposite. This composite was characterized using XRD, FTIR, SEM, BET, and XPS. The results indicate that the morphology of the ZnS-PANI nanocomposite possesses a uniform spherical shape. The ZnS-PANI electrode shows an excellent initial discharge capacity of 1182.1 mAh/g, a high discharge capacity of 693.5 mAh/g at a current rate of 0.1 °C after 500 cycles, good cycling stability, and an excellent rate capability of 673 mAh/g at 2.0 °C, when used as anode materials for lithium-ion batteries (LIBs). The excellent electrochemical performances make the nanosized ZnS-PANI nanocomposite a promising candidate for the LIBs.

     

Porous Carbon Nanofibers Encapsulated with Peapod‐Like Hematite Nanoparticles for High‐Rate and Long‐Life Battery Anodes

Fe₂O₃ is regarded as a promising anode material for lithium‐ion batteries (LIBs) and sodium‐ion batteries (SIBs) due to its high specific capacity. The large volume change during discharge and charge processes, however, induces significant cracking of the Fe₂O₃ anodes, leading to rapid fading of the capacity. Herein, a novel peapod‐like nanostructured material, consisting of Fe₂O₃ nanoparticles homogeneously encapsulated in the hollow interior of N‐doped porous carbon nanofibers, as a high‐performance anode material is reported. The distinctive structure not only provides enough voids to accommodate the volume expansion of the pea‐like Fe₂O₃ nanoparticles but also offers a continuous conducting framework for electron transport and accessible nanoporous channels for fast diffusion and transport of Li/Na‐ions. As a consequence, this peapod‐like structure exhibits a stable discharge capacity of 1434 mAh g^?1 (at 100 mA g^?1) and 806 mAh g^?1 (at 200 mA g^?1) over 100 cycles as anode materials for LIBs and SIBs, respectively. More importantly, a stable capacity of 958 mAh g^?1 after 1000 cycles and 396 mAh g^?1 after 1500 cycles can be achieved for LIBs and SIBs, respectively, at a large current density of 2000 mA g^?1. This study provides a promising strategy for developing long‐cycle‐life LIBs and SIBs.     

四氧化三钴/碳纳米管薄膜的水热合成及其储锂性能

以5-磺基水杨酸和戊二酸为螯合和氧化试剂,在水热条件下将硫酸钴氧化成纳米级Co₃O₄。以碳纳米管薄膜为载体将Co₃O₄颗粒紧密地附着在碳纳米管上使其填充入碳纳米管薄膜的空隙生成Co₃O₄/碳纳米管复合材料薄膜(Co₃O₄@CNTs),并研究其储锂性能。电化学测试结果表明,Co₃O₄@CNTs薄膜具有较高的放电比容量和优异的倍率性能,在0.2C倍率下初始放电比容量高达1712.5 mAh·g^-1,100圈循环后放电比容量为1128.9 mAh·g^-1的;在1C倍率下100圈循环后放电比容量仍然保持527.8 mAh·g^-1。Co₃O₄@CNTs薄膜优异的性能源于Co₃O₄与CNTs的协同作用。高分散性的Co₃O₄增大了活性材料与电解液之间的接触面积,CNTs有助于形成良好的导电网络提高电子电导率,进而提高了Co₃O₄负极材料的循环性能和倍率性能。     

Amorphous Sn modified nitrogen-doped porous carbon nanosheets with rapid capacitive mechanism for high-capacity and fast-charging lithium-ion batteries

Sn-based materials are considered as a kind of potential anode materials for lithium-ion batteries (LIBs) owing to their high theoretical capacity. However, their use is limited by large volume expansion deriving from the lithiation/delithiation process. In this work, amorphous Sn modified nitrogen-doped porous carbon nanosheets (ASn-NPCNs) are obtained. The synergistic effect of amorphous Sn and high edge-nitrogen-doped level porous carbon nanosheets provides ASn-NPCNs with multiple advantages containing abundant defect sites, high specific surface area (214.9 m²·g⁻¹), and rich hierarchical pores, which can promote the lithium-ion storage. Serving as the LIB anode, the as-prepared ASn-NPCNs-750 electrode exhibits an ultrahigh capacity of 1643 mAh·g⁻¹ at 0.1 A·g⁻¹, ultrafast rate performance of 490 mAh·g⁻¹ at 10 A·g⁻¹, and superior long-term cycling performance of 988 mAh·g⁻¹ at 1 A·g⁻¹ after 2000 cycles with a capacity retention of 98.9%. Furthermore, the in-depth electrochemical kinetic test confirms that the ultrahigh-capacity and fast-charging performance of the ASn-NPCNs-750 electrode is ascribed to the rapid capacitive mechanism. These impressive results indicate that ASn-NPCNs-750 can be a potential anode material for high-capacity and fast-charging LIBs.     

原位聚合导电高分子包混对硬碳性能的影响

采用原位聚合方法对硬碳材料进行了导电聚合物包混,并测试了导电聚合物包混硬碳材料的电化学性能.利用扫描电镜,拉曼光谱,电导率仪及恒电流法研究了导电聚合物包混的硬碳材料的结构以及充放电特性.研究发现,聚苯胺、聚吡咯和聚噻吩等均能通过原位聚合包混在硬碳表面.其中,采用噻吩在硬碳表面原位聚合增强了硬碳材料的导电性.经聚噻吩包混的硬碳首次充电容量达到了385mAh g-1以上,高于未包混的硬碳(320mAh g-1).循环20周以后聚噻吩包混硬碳的容量仍保持在325 mAh g-1以上,而未包混硬碳的容量则降低到290 mAh g-1以下.     

Efficient Laser‐Induced Construction of Oxygen‐Vacancy Abundant Nano‐ZnCo2O4/Porous Reduced Graphene Oxide Hybrids toward Exceptional Capacitive Lithium Storage

Recently, binary ZnCo₂O₄ has drawn enormous attention for lithium‐ion batteries (LIBs) as attractive anode owing to its large theoretical capacity and good environmental benignity. However, the modest electrical conductivity and serious volumetric effect/particle agglomeration over cycling hinder its extensive applications. To address the concerns, herein, a rapid laser‐irradiation methodology is firstly devised toward efficient synthesis of oxygen‐vacancy abundant nano‐ZnCo₂O₄/porous reduced graphene oxide (rGO) hybrids as anodes for LIBs. The synergistic contributions from nano‐dimensional ZnCo₂O₄ with rich oxygen vacancies and flexible rGO guarantee abundant active sites, fast electron/ion transport, and robust structural stability, and inhibit the agglomeration of nanoscale ZnCo₂O₄, favoring for superb electrochemical lithium‐storage performance. More encouragingly, the optimal L‐ZCO@rGO‐30 anode exhibits a large reversible capacity of ≈1053 mAh g^?1 at 0.05 A g^?1, excellent cycling stability (≈746 mAh g^?1 at 1.0 A g^?1 after 250 cycles), and preeminent rate capability (≈686 mAh g^?1 at 3.2 A g^?1). Further kinetic analysis corroborates that the capacitive‐controlled process dominates the involved electrochemical reactions of hybrid anodes. More significantly, this rational design holds the promise of being extended for smart fabrication of other oxygen‐vacancy abundant metal oxide/porous rGO hybrids toward advanced LIBs and beyond.     

Superior performance for lithium storage from an integrated composite anode consisting of SiO-based active material and current collector

Silicon-based material is considered to be one of the most promising anodes for the next-generation lithium-ion batteries (LIBs) due to its rich sources, non-toxicity, low cost and high theoretical specific capacity. However, it cannot maintain a stable electrode structure during repeated charge/discharge cycles, and therefore long cycling life is difficult to be achieved. To address this problem, herein a simple and efficient method is developed for the fabrication of an integrated composite anode consisting of SiO-based active material and current collector, which exhibits a core–shell structure with nitrogen-doped carbon coating on SiO/P micro-particles. Without binder and conductive agent, the volume expansion of SiO active material in the integrated composite anode is suppressed to prevent its pulverization. At a current density of 500 mA·g⁻¹, this integrated composite anode exhibits a reversible specific capacity of 458 mA·h·g⁻¹ after 200 cycles. Furthermore, superior rate performance and cycling stability are also achieved. This work illustrates a potential method for the fabrication of integrated composite anodes with superior electrochemical properties for high-performance LIBs.     

Simple synthesis of a porous Sb/Sb2O3 nanocomposite for a high-capacity anode material in Na-ion batteries

High-capacity anode materials are highly desirable for sodium ion batteries.Here,a porous Sb/Sb2O3 nanocomposite is successfully synthesized by the mild oxidization of Sb nanocrystals in air.In the composite,Sb contributes good conductivity and Sb2O3 improves cycling stability,particularly within the voltage window of 0.02-1.5 V.It remains at a reversible capacity of 540 mAh·g-1 after 180 cycles at 0.66 A·g-L Even at 10 A·g-1,the reversible capacity is still preserved at 412 mAh.g-1,equivalent to 71.6％ of that at 0.066 A.g-1.These results are much better than Sb nanocrystals with a similar size and structure.Expanding the voltage window to 0.02-2.5 V includes the conversion reaction between Sb2O3 and Sb into the discharge/charge profiles.This would induce a large volume change and high structure strain/stress,deteriorating the cycling stability.The identification of a proper voltage window for Sb/Sb2O3 paves the way for its development in sodium ion batteries.     

A novel type of Ge nanotube arrays for lithium storage material

Amorphous Ge nanotubes, featured of a top-closed tubular structure, were synthesized directly on metallic current collector substrates via a template technique. Measurement of electrochemical cycling reveals that these nanotubes can deliver reversible capacities of -1300 mAh/g (81% of the theoretical capacity) at the current density of C/20 (1C = 1600 mAh/g) and retain -700 mAh/g at 2C with columbic efficiencies over 99%. Such performance is comparable to that of the recently reported Ge nanowire anodes grown directly on the metallic substrates by the chemical vapor deposition, indicating that the present Ge nanotubes are a type of anode materials with high capacity and good rate performance for lithium storage.     

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.     

Three-Dimensional Self-assembled Hairball-Like VS4 as High-Capacity Anodes for Sodium-Ion Batteries

Sodium-ion batteries(SIBs)are considered to be attractive candidates for large-scale energy storage systems because of their rich earth abundance and consistent performance.However,there are still challenges in developing desirable anode materials that can accommodate rapid and stable insertion/extraction of Na+and can exhibit excellent electrochemical performance.Herein,the self-assembled hairball-like VS4 as anodes of SIBs exhibits high discharge capacity(660 and 589 mAh g−1 at 1 and 3 A g−1,respectively)and excellent rate property(about 100%retention at 10 and 20 A g−1 after 1000 cycles)at room temperature.Moreover,the VS4 can also exhibit 591 mAh g−1 at 1 A g−1 after 600 cycles at 0°C.An unlike traditional mechanism of VS4 for Na+storage was proposed according to the dates of ex situ characterization,cyclic voltammetry,and electrochemical kinetic analysis.The capacities of the final stabilization stage are provided by the reactions of reversible transformation between Na2S and S,which were considered the reaction mechanisms of Na–S batteries.This work can provide a basis for the synthesis and application of sulfur-rich compounds in fields of batteries,semiconductor devices,and catalysts.     

One-step fabrication of two-dimensional hierarchical Mn2O3@graphene composite as high-performance anode materials for lithium ion batteries

Two-dimensional (2D) hierarchical Mn2O3@graphene composite is synthesized by a one-step solid-phase reaction.The nanosheets of Mn2O3 are vertically grown on few-layered graphene,constructing a unique 2D hierarchical structure.As an anode material for lithium-ion batteries (LIBs),this hierarchical composite displays excellent electrochemical performances,showing an extraordinary reversible discharge capacity of 2125.9 mA h g-1.Moreover,a record high reversible capacity of 1746.8 mA h g-1 is maintained after 100 cycles at a current density of 100 mA g-1,which retains 82.2 ％ of the initial capacity.Such an outstanding performance could be attributed to its novel structure and the synergistic effects between the Mn2O3 and graphene.     

Core–Shell Si/C Nanospheres Embedded in Bubble Sheet‐like Carbon Film with Enhanced Performance as Lithium Ion Battery Anodes

Due to its high theoretical capacity and low lithium insertion voltage plateau, silicon has been considered one of the most promising anodes for high energy and high power density lithium ion batteries (LIBs). However, its rapid capacity degradation, mainly caused by huge volume changes during lithium insertion/extraction processes, remains a significant challenge to its practical application. Engineering Si anodes with abundant free spaces and stabilizing them by incorporating carbon materials has been found to be effective to address the above problems. Using sodium chloride (NaCl) as a template, bubble sheet‐like carbon film supported core–shell Si/C composites are prepared for the first time by a facile magnesium thermal reduction/glucose carbonization process. The capacity retention achieves up to 93.6% (about 1018 mAh g^?1) after 200 cycles at 1 A g^?1. The good performance is attributed to synergistic effects of the conductive carbon film and the hollow structure of the core–shell nanospheres, which provide an ideal conductive matrix and buffer spaces for respectively electron transfer and Si expansion during lithiation process. This unique structure decreases the charge transfer resistance and suppresses the cracking/pulverization of Si, leading to the enhanced cycling performance of bubble sheet‐like composite.