Self-assembled reduced graphene oxide/sulfur composite encapsulated by polyaniline for enhanced electrochemistry performance

Reduced graphene oxide/sulfur/polyaniline (referred to RGO/S/PANI) composite was self-assembled through in situ synthesis and used to investigate the electrochemical properties of lithium/sulfur cells. The RGO/S/PANI composite possessed 809.3/801.9 mAh g^?1 of initial charge/discharge capacities, higher than 588.3/588.2 mAh g^?1 for reduced graphene oxide/sulfur (referred to RGO/S) and 681.4/669.9 mAh g^?1 for sulfur/polyaniline (referred to S/PANI) at similar conditions. The RGO/S/PANI composite obtained 400 mAh g^?1 at 2 C and good reversible capacities of 605.5 and 600.8 mAh g^?1 at 100th charge/discharge cycle at 0.1 C, in comparison with low electrochemical performance of RGO/S and S/PANI. The improved properties could be attributed to the collaboration of RGO and PANI. Co-generation of RGO and sulfur acted as seeds for their depositions, stimulated their uniform distributions, and restricted the agglomeration of sulfur particles in situ synthesis. Polyaniline coated RGO/S and stabilized the nanostructure of RGO/S/PANI in repeated charge/discharge cycles. In addition, RGO and PANI provided many electron channels to enhance sulfur conductivity and sufficient void space for sulfur swelling during charge/discharge cycles.     

One-step hydrothermal synthesis of flower-like SnO2/carbon nanotubes composite and its electrochemical properties

In this work, flower-like SnO₂/carbon nanotubes (CNTs) composite was synthesized by one-step hydrothermal method for high-capacity lithium storage. The microstructures of products were characterized by XRD, FESEM and TEM. The electrochemical performance of the flower-like SnO₂/CNTs composite was measured by cyclic voltammetry and galvanostatic charge/discharge cycling. The results show that the flower-like SnO₂/CNTs composite displays superior Li-battery performance with large reversible capacity and high rate capability. The first discharge and charge capacities are 1,230 and 842 mAh g^?1, respectively. After 40 cycles, the reversible discharge capacity is still maintained at 577 mAh g^?1 at the current densities of 50, 100 and 500 mA g^?1, indicating that it’s a promising anode material for high performance lithium-ion batteries.     

Polyaniline encapsulated silicon nanocomposite as high-performance anode materials for lithium ion batteries

Polyaniline encapsulated silicon (Si/PANI) nanocomposite as anode materials for high-capacity lithium ion batteries has been prepared by an in situ chemical polymerization of aniline monomer in the suspension of Si nanoparticles. The obtained Si/PANI nanocomposite demonstrates a reversible specific capacity of 840 mAh g^?1 after 100 cycles at a rate of 100 mA g^?1 and excellent cycling stability. The enhanced electrochemical performance can be due to that the polyaniline (PANI) matrix offers a continuous electrically conductive network as well as enhances the compatibility of electrode materials and electrolyte as a result of suppressing volume stress of Si during cycles and preventing the agglomeration of Si nanoparticles.     

SnO2 sheet/graphite composite as anode material with improved electrochemical performance for lithium-ion batteries

The SnO₂ sheet/graphite composite was synthesized by a hydrothermal method for high-capacity lithium storage. The microstructures of products were characterized by XRD and FE-SEM. The electrochemical performance of SnO₂ sheet/graphite composite was measured by galvanostatic charge/discharge cycling and EIS. The first discharge and charge capacities are 1,072 and 735 mAh g^?1 with coulombic efficiency of 68.6 %. After 40 cycles, the reversible discharge capacity is still maintained at 477 mAh g^?1. The results show that the SnO₂ sheet/graphite composite displays superior Li-battery performance with large reversible capacity and good cyclic performance.     

Pyrrolic nitrogen-doped carbon sandwiched monolayer MoS<Subscript>2</Subscript> vertically anchored on graphene oxide for high-performance sodium-ion battery anodes

In this work, a novel pyrrolic nitrogen-doped carbon sandwiched monolayer MoS₂ hybrid was prepared. This sandwiched hybrid vertically anchors on graphene oxide as anode materials for sodium-ion batteries. Such electrode was fabricated by facile ionic liquid-assisted reflux and annealing methods. Owing to rational structure and enhancement from pyrrolic nitrogen dopant, this unique MoS₂/C-graphene hybrid exhibits reversible specific capacity of 486 mAh g^?1 after 1000 cycles with a low average fading capacity of 0.15 mAh g^?1 (fading cyclic rate of ca. 0.03% per cycle). A capacity of 330 mAh g^?1 is remained at the current densities of 10.0 A g^?1. The proposed strategy provides a convenient way to create new pyrrolic nitrogen-doped hybrids for energy field and other related applications.     

Stability electrochemical performance of self-assembled hierarchical MnCO<Subscript>3</Subscript>/MWCNT nanocomposite as anode material for lithium-ion batteries

The self-assembled hierarchical MnCO₃/MWCNT nanoarchitectures are prepared by a facile solvothermal method and used as anode material for lithium-ion batteries. The results of SEM and TEM show that the hierarchical nanorods are made of the primary MnCO₃ nanocrystals. The hierarchical nanorods MnCO₃ are heterogeneously distributed among retiform MWCNTs. Those MnCO₃/MWCNT nanoarchitectures are able to buffer the physical aggregation of the MnCO₃ nanorods and volume expansion of MnCO₃ in the charge/discharge process. The self-assembled hierarchical MnCO₃/MWCNT nanocomposite delivers a reversible capacity of 704 mAh g^?1 after 110 cycles at a current density of 100 mA g^?1. The excellent electrochemical performance is attributed to the self-assembled hierarchical MnCO₃/MWCNT nanoarchitectures and the high conductivity of MWCNTs.     

Electrochemical performance of LiMn2O4 microcubes prepared by a self-templating route

LiMn₂O₄ microcubes with a size of 10–15 μm have been synthesized by a facile self-templating route starting from cubic MnCO₃. The LiMn₂O₄ microcubes exhibit a hierarchical structure, where the cubes are stacked from parallel plates with a thickness of 200 nm, where each plate is composed of interconnected nanoparticles with a size of around 200 nm. The cubic LiMn₂O₄ shows excellent rate capability and high-rate cycling stability. At 10 C, it can yield a discharge capacity of 108 mAh g^?1. A discharge capacity of 88 mAh g^?1 can be retained after 100 cycles at 10 C. The excellent electrochemical performance makes it a promising cathode for high-power Li-ion batteries.     

Cathode material for sodium-ion batteries based on manganese hexacyanoferrate: the role of the binder component

Sodium manganese hexacyanoferrate (NaMnHCF) was synthesized by a hydrothermal method and investigated as a cathode material for sodium-ion batteries. The morphology and the structure of NaMnHCF were investigated by X-ray diffraction, scanning electron microscopy, and EDX analysis. New composition of NaMnHCF cathode material for sodium-ion batteries with eco-friendly water-based binder consisting of conducting polymer poly-3,4-ethylenedioxythiopene/polystyrene sulfonate (PEDOT:PSS) dispersion and carboxymethyl cellulose (СМС) was proposed. The electrochemical properties of NaMnHCF cathode material with conductive polymer binder were investigated by cyclic voltammetry and galvanostatic charge-discharge, and the results were compared with the performance of a conventional PVDF-bound material. It was shown that the initial discharge capacity of electrodes with conductive binder is 130 mAh g⁻¹, whereas the initial discharge capacity of PVDF-bound electrodes was 109 mAh g⁻¹ (both at current density 120 mA g⁻¹, values normalized by NaMnHCF mass). The material with conductive binder also has better rate capability; however, it is losing in cycling capability to the electrode composition with conventional PVDF binder.

     

Synthesis of spherical porous carbon by spray pyrolysis and its application in Li-S batteries

A spherical porous carbon (SPC) with high specific surface area is prepared by spray pyrolysis at 800 °C followed by removing silica template. The prepared SPC is employed as a conductive matrix in the sulfur cathode (S-SPC) for lithium–sulfur secondary batteries. The BET surface area of the prepared SPC sample is as high as 1,133 m² g^?1 and the total pore volume is 2.75 cm³ g^?1. The electrochemical evaluations including charge–discharge tests, cyclic voltammograms (CV), and electrochemical impedance spectrum suggest that the prepared S-SPC composite presents superior electrochemical stability when compared to the S-SP cathode. The as-prepared S-SPC composite shows improved cycle performance. The reversible discharge capacity is about 637 mAh g^?1 after 50 cycles, which is much better than that of the as-prepared sulfur–Super P carbon black composite. It may be attributed to the high porosity and excellent conductive structure of the SPC.     

A Yolk–Shell-Structured FePO4 Cathode for High-Rate and Long-Cycling Sodium-Ion Batteries

Amorphous iron phosphate (FePO₄) has attracted enormous attention as a promising cathode material for sodium-ion batteries (SIBs) because of its high theoretical specific capacity and superior electrochemical reversibility. Nevertheless, the low rate performance and rapid capacity decline seriously hamper its implementation in SIBs. Herein, we demonstrate a sagacious multi-step templating approach to skillfully craft amorphous FePO₄ yolk–shell nanospheres with mesoporous nanoyolks supported inside the robust porous outer nanoshells. Their unique architecture and large surface area enable these amorphous FePO₄ yolk–shell nanospheres to manifest remarkable sodium storage properties with high reversible capacity, outstanding rate performance, and ultralong cycle life.     

Tin nanoparticles embedded in ordered mesoporous carbon as high-performance anode for sodium-ion batteries

Tin (Sn) has been considered as an attractive anode material for sodium-ion batteries (SIBs) due to its high theoretical capacity (847 mAh g^?1). Nevertheless, its low conductivity and large volume change during cycling essentially prevent the possibility of high capacity and long-term cycle for SIBs. In this work, Sn nanoparticles are well embedded into the highly ordered mesoporous carbon (CMK-3) matrix (Sn@CMK-3) using a facile sonochemical method combined with heat treatment. The resultant Sn@CMK-3 nanohybrid electrode delivers an initial charge capacity of 412 mAh g^?1 at 100 mA g^?1. A reversible capacity of 337 mAh g^?1 is obtained after 200 cycles, indicating the good cycle stability of the nanohybrid structure. The electrode also shows a potential rate capability, which maintains a capacity of 228 mAh g^?1 at 1000 mA g^?1. When the current density returns to 50 mA g^?1, the capacity goes back to 381 mAh g^?1, with a capacity retention of 86.9%. The enhanced sodium storage performance of Sn@CMK-3 nanohybrid can be related to the synergistic effect between CMK-3 and Sn.

Open image in new window

Graphical abstract Sn@CMK-3 nanohybrid with Sn nanoparticles uniformly distributed into the highly ordered mesoporous carbon matrix exhibited good cycling performance and rate capability.

     

Facile synthesis of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> microsheets with porous micro-nanostructure as high-rate cathode materials for Li-ion batteries

Porous LiMn₂O₄ microsheets with micro-nanostructure have been successfully prepared through a simple carbon gel-combustion process with a microporous membrane as hard template. The crystal structure, morphology, chemical composition, and surface analysis of the as-obtained LiMn₂O₄ microsheets are characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscope (XPS). It can be found that the as-prepared LiMn₂O₄ sample presents the two-dimensional (2-D) sheet structure with porous structure comprised with nano-scaled particles. As cathode materials for lithium-ion batteries, the obtained LiMn₂O₄ microsheets show superior rate capacities and cycling performance at various charge/discharge rates. The LiMn₂O₄ microsheets exhibit a higher charge and discharge capacity of 137.0 and 134.7 mAh g^?1 in the first cycle at 0.5 C, and it remains 127.6 mAh g^?1 after 50 cycles, which accounts for 94.7% discharge capacity retention. Even at 10 C rate, the electrode also delivers the discharge capacity of 91.0 mAh g^?1 after 300 cycles (93.5% capacity retention). The superior electrochemical properties of the LiMn₂O₄ microsheets could be attributed to the unique microsheets with porous micro-nanostructure, more active sites of the Li-ions insertion/deinsertion for the higher contact area between the LiMn₂O₄ nano-scaled particles and the electrolyte, and better kinetic properties, suggesting the applications of the sample in high-power lithium-ion batteries.     

Mesoporous carbon/sulfur composite with N-doping and tunable pore size for high-performance Li-S batteries

Mesoporous carbons (MCs) were used as the matrixes to load sulfur for lithium sulfur (Li-S) batteries, and pore sizes were tuned by heat treatment at different high temperatures. The cathode material shows the highest discharge capacity of 1158.2 mAh g^?1 at the pore size of 4.1 nm among as-prepared nitrogen-free materials with different sizes. Meanwhile, the nitrogen doping of mesoporous carbon helps to inhibit the diffusion of polysulfide species via an enhanced surface adsorption. The carbon/sulfur containing N (4.56%) shows a high initial discharge capacity of 1315.8 mAh g^?1 and retains about 939 mAh g^?1 after 100 cycles at 0.2 C. The improved electrochemical performance is ascribed to the proper pore size, surface chemical property, and conductivity of the N-doped carbon material.     

Simple chemical route for nanorod-like cobalt oxide films for electrochemical energy storage applications

We used a simple chemical synthesis route to deposit nanorod-like cobalt oxide thin films on different substrates such as stainless steel (ss), indium tin oxide (ITO), and microscopic glass slides. The morphology of the films show that the films were uniformly spread having a nanorod-like structure with the length of the nanorods shortened on ss substrates. The electrochemical properties of the films deposited at different time intervals were studied using cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), and electrochemical impedance spectroscopy (EIS). The film deposited after 20 cycles on ss gave the highest specific capacity of 67.6 mAh g^?1 and volumetric capacity of 123 mAh cm^?3 at a scan rate 5 mV s^?1 in comparison to 62.0 mAh g^?1 and 113 mAh cm^?3 obtained, respectively, for its counterpart on ITO. The film electrode deposited after 20 cycles on ITO gave the best rate capability and excellent cyclability with no depreciation after 2000 charge–discharge cycles.     

Electrospun Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>/Li<Subscript>2</Subscript>TiO<Subscript>3</Subscript> composite nanofibers for enhanced high-rate lithium ion batteries

Li₄Ti₅O₁₂/Li₂TiO₃ composite nanofibers with the mean diameter of ca. 60 nm have been synthesized via facile electrospinning. When the molar ratio of Li to Ti is 4.8:5, the Li₄Ti₅O₁₂/Li₂TiO₃ composite nanofibers exhibit initial discharge capacity of 216.07 mAh g^?1 at 0.1 C, rate capability of 151 mAh g^?1 after being cycled at 20 C, and cycling stability of 122.93 mAh g^?1 after 1000 cycles at 20 C. Compared with pure Li₄Ti₅O₁₂ nanofibers and Li₂TiO₃ nanofibers, Li₄Ti₅O₁₂/Li₂TiO₃ composite nanofibers show better performance when used as anode materials for lithium ion batteries. The enhanced electrochemical performances are explained by the incorporation of appropriate Li₂TiO₃ which could strengthen the structure stability of the hosted materials and has fast Li⁺-conductor characteristics, and the nanostructure of nanofibers which could offer high specific area between the active materials and electrolyte and shorten diffusion paths for ionic transport and electronic conduction. Our new findings provide an effective synthetic way to produce high-performance Li₄Ti₅O₁₂ anodes for lithium rechargeable batteries.     

Engineering Active Sites of Polyaniline for AlCl2+ Storage in an Aluminum‐Ion Battery

The reversible capacity of AlCl₄^? intercalation/de‐intercalation in conventional cathodes of aluminum‐ion batteries (AIBs) is difficult to improve due to the large size of AlCl₄^? anions. Therefore, it is highly desirable to realize the intercalation/de‐intercalation of smaller Al‐based ions. Here, we fabricated polyaniline/single‐walled carbon nanotubes (PANI/SWCNTs) composite films and protonated the PANI nanorods. The protonation endows PANI with more active sites and enhanced conductivity. Hyper self‐protonated PANI (PANI(H⁺)) exhibits reversible AlCl₂⁺ intercalation/de‐intercalation during the discharge/charge process. As a result, the discharge capacity of the Al/PANI(H⁺) battery is twice as high as that of the initial composite films. PANI(H⁺)@SWCNT electrodes also have a stable cycling life with only 0.003 % capacity decay per cycle over 8000 cycles. Owing to the excellent mechanical properties, PANI(H⁺)@SWCNT composite films can act as the electrodes of flexible AIBs.     

Polymer template-assisted microemulsion synthesis of large surface area, porous Li2MnO3 and its characterization as a positive electrode material of Li-ion cells

Lithium-rich manganese oxide (Li₂MnO₃) is prepared by reverse microemulsion method employing Pluronic acid (P123) as a soft template and studied as a positive electrode material. The as-prepared sample possesses good crystalline structure with a broadly distributed mesoporosity but low surface area. As expected, cyclic voltammetry and charge–discharge data indicate poor electrochemical activity. However, the sample gains surface area with narrowly distributed mesoporosity and also electrochemical activity after treating in 4 M H₂SO₄. A discharge capacity of about 160 mAh g^?1 is obtained. When the acid-treated sample is heated at 300 °C, the resulting porous sample with a large surface area and dual porosity provides a discharge capacity of 240 mAh g^?1. The rate capability study suggests that the sample provides about 150 mAh g^?1 at a specific discharge current of 1.25 A g^?1. Although the cycling stability is poor, the high rate capability is attributed to porous nature of the material.     

Lithium garnet based free-standing solid polymer composite membrane for rechargeable lithium battery

Electrolytes with high lithium-ion conductivity, better mechanical strength and large electrochemical window are essential for the realization of high-energy density lithium batteries. Polymer electrolytes are gaining interest due to their inherent flexibility and nonflammability over conventional liquid electrolytes. In this work, lithium garnet composite polymer electrolyte membrane (GCPEM) consisting of large molecular weight (W_avg ~?5?×?10⁶) polyethylene oxide (PEO) complexed with lithium perchlorate (LiClO₄) and lithium garnet oxide Li_6.28Al_0.24La₃Zr₂O₁₂ (Al-LLZO) is prepared by solution-casting method. Significant improvement in Li⁺ conductivity for Al-LLZO containing GCPEM is observed compared with the Al-LLZO free polymer membrane. Maximized room temperature (30 °C) Li⁺ conductivity of 4.40?×?10^?4 S cm^?1 and wide electrochemical window (4.5 V) is observed for PEO₈/LiClO₄?+?20 wt% Al-LLZO (GCPEM-20) membrane. The fabricated cell with LiCoO₂ as cathode, metallic lithium as anode and GCPEM-20 as electrolyte membrane delivers an initial charge/discharge capacity of 146 mAh g^?1/142 mAh g^?1 at 25 °C with 0.06 C-rate.     

Activated carbon aerogels with high bimodal porosity for lithium/sulfur batteries

Activated carbon aerogels (ACAs) with high bimodal porosity were obtained for lithium/sulfur batteries by potassium hydroxide (KOH) activation. Then sulfur–activated carbon aerogels (S–ACAs) composites were synthesized by chemical deposition strategy. The S–ACAs composites were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy, and N₂ adsorption/desorption measurements. It is found that the activated carbon aerogels treated by KOH activation presents a porous structure, and sulfur is embedded into the pores of the ACAs network-like matrix after a chemical deposition process. The Li/S–ACAs (with 69.1 wt% active material) composite cathode exhibits discharge capacities of 1,493 mAh g^?1 in the first cycle and 528 mAh g^?1 after 100 cycles at a higher rate of C/5 (335 mA g^?1). The S–ACAs composite cathode exhibits better electrochemical reversibility, higher active material utilization, and less severe polysulfide shuttle than S–CAs composite cathode because of high bimodal porosity structure of the ACAs matrix.     

Na2FePO4F/Biocarbon Nanocomposite Hollow Microspheres Derived from Biological Cell Template as High-Performance Cathode Material for Sodium-Ion Batteries

We have successfully synthesized Na₂FePO₄F/biocarbon nanocomposite hollow microspheres from Fe^III precursor as cathodes for sodium-ion batteries through self-assembly of yeast cell biotemplate and sol-gel technology. The carbon coating on the nanoparticle surface with a mesoporous structure enhances electron diffusion into Na₂FePO₄F crystal particles. The improved electrochemical performance of Na₂FePO₄F/biocarbon nanocomposites is attributed to the larger electrode−electrolyte contact area and more active sites for Na⁺ on the surface of hollow microspheres compared with those of Na₂FePO₄F/C. The Na₂FePO₄F/biocarbon nanocomposite exhibits a high initial discharge capacity of 114.3 mAh g⁻¹ at 0.1 C, long-cycle stability with a capacity retention of 74.3 % after 500 cycles at 5 C, and excellent rate capability (70.2 mAh g⁻¹ at 5 C) compared with Na₂FePO₄F/C. This novel nanocomposite hollow microsphere structure is suitable for improving the property of other cathode materials for high-power batteries.