A twins-structural Sn@C core–shell composite as anode materials for lithium-ion batteries

In this paper, we report a facile method to prepare a twins-structural Sn@C core–shell composite that is used as anode materials for lithium-ion batteries. Its surface morphology and microstructures were characterized by the scanning electron microscope, X-ray diffraction, and transmission electron microscope. The electrochemical performances of Sn@C were measured by charge–discharge tests, cyclic voltammogram, and electrochemical impedance spectra. It is shown that such a composite exhibits a high initial specific capacity of 970 mA h g^?1 and a capacity retention of 400 mA h g^?1 after 50 cycles at the current density of 100 mA g^?1.     

Preparation of C/Ni–NiO composite nanofibers for anode materials in lithium-ion batteries

We report here on a systematic study about the formation of laser-induced periodic surface structures (LIPSS) on biopolymers. Self-standing films of the biopolymers chitosan, starch and the blend of chitosan with the synthetic polymer poly (vinyl pyrrolidone), PVP, were irradiated in air with linearly polarized laser beams at 193, 213 and 266 nm, with pulse durations in the range of 6–17 ns. The laser-induced periodic surface structures were topographically characterized by atomic force microscopy and the chemical modifications induced by laser irradiation were inspected via Raman spectroscopy. Formation of LIPSS parallel to the laser polarization direction, with periods similar to the laser wavelength, was observed at efficiently absorbed wavelengths in the case of the amorphous biopolymer chitosan and its blend with PVP, while formation of LIPSS is prevented in the crystalline starch biopolymer.     

Novel silicon–oxygen–carbon composite with excellent cycling steady performance as anode for lithium-ion batteries

The novel anode material for lithium-ion batteries, silicon–oxygen–carbon (Si–O–C) composite, is prepared by a liquid solidification combined with following pyrolysis process, in which silicon dioxide (SiO₂) is used as an additive agent to enhance the electrochemical performance of the composite. While the structure of the composite is confirmed by X-ray diffraction (XRD) and Fourier transform infrared spectra (FT-IR), the morphology and microstructure were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), respectively. SEM and TEM observations reveal that the Si–O–C powders are about 1 μm in diameter, and there is a homogenous pyrolyzed carbon layer about 5 nm thick on the surface of the particle. The Si–O–C sample as anode material can deliver a high initial charge capacity of 753.4 mAh g^?1, and the capacity keeps above 500.0 mAh g^?1 after 40 cycles at 100.0 mA g^?1. The electrochemical impedance spectroscopy results show that the composite exhibits lower charge transfer resistance and higher lithium-ion diffusion rate compared with the Si–C anode, which indicates that the composite Si–O–C could be used as a promising anode material for lithium-ion batteries.

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Graphical Abstract SEM images of the Si-C (a) and Si-O-C (b) samples and the TEM (c) and HRTEM (d) image of the Si-O-C sample

     

Preparation and performance of sulfur–carbon composite based on hollow carbon nanofiber for lithium-sulfur batteries

A unique structured hollow carbon nanofiber–sulfur composite material (HCF–S) was fabricated and characterized in lithium-sulfur batteries. It is found that a part of spherical sulfur particles are located in the voids formed by the intertwined fibers and the others are confined in hollow channel of the HCF. The high conductive and porous HCF favors the construction of stable three-dimensional conducting network and convenient infiltration of the electrolytes into the cathode. The HCF–S cathode exhibits excellent electrochemical performance in the electrolyte with LiNO₃. By contrast, the ionic liquid electrolyte provides insufficient shuttle suppression and weakens ion transport, which leads to poor cycle and rate capability.     

PVC–PMMA composite electrospun membranes as polymer electrolytes for polymer lithium-ion batteries

Composite nanofibrous membranes based on poly (vinyl chloride) (PVC)?Cpoly (methyl methacrylate) (PMMA) were prepared by electrospinning and then they were soaked in liquid electrolyte to form polymer electrolytes (PEs). The introduction of PMMA into the PVC matrix enhanced the compatibility between the polymer matrix and the liquid electrolyte. The composite nanofibrous membranes prepared by electrospinning involved a fully interconnected pore structure facilitating high electrolyte uptake and easy transport of ions. The ion conductivity of the PEs increased with the increase in PMMA content in the blend and the ion conductivity of the polymer electrolyte based on PVC?CPMMA (5:5, w/w) blend was 1.36?×?10^?3 S cm^?1 at 25?°C. The polymer electrolyte based on PVC?CPMMA (5:5, w/w) blend presented good electrochemical stability up to 5.0?V (vs. Li/Li⁺) and good interfacial stability with the lithium electrode. The promising results showed that nanofibrous PEs based on PVC?CPMMA were of great potential application in polymer lithium-ion batteries.     

Cellulose-based carbon—A potential anode material for lithium-ion battery

A series of hard carbons was produced by the carbonization of microcrystalline cellulose powder in the temperature range of 950–1100 °C. The properties of the carbons were characterized using elemental analysis, X-ray diffraction and N₂ and CO₂ adsorption. The effect of heat-treatment temperature (HTT), pyrolytic carbon (PC) coating and discharging mode on the lithium insertion/deinsertion behavior of the carbons was assessed in a coin-type half-cell with metal lithium cathode. Increasing cellulose HTT modifies mostly carbon porosity, the surface area (S_DFT) decreases from about 500 to 167 m² g⁻¹. It is associated with lowering the reversible C_rev and irreversible C_irr capacities, but without improving relatively low (0.72) 1st cycle coulombic efficiency. Applying constant current (CC)+constant voltage (CV) discharging mode instead of conventional CC enhances the reversible capacity by 15–18%. PC coating is effective in reducing C_irr by ∼20% with a little change of C_rev. The best capacity parameters, C_rev of 458 mA h g⁻¹ and C_irr of 139 mA h g⁻¹, were measured for PC coated 1000 °C carbon. The prolonged cycling of full-cell assembled with anode of the carbon and commercial cathode revealed that after initial 20 cycles the capacity decay (0.029 mA h/cycle) is comparable to that of commercial cell with graphite-based anode.     

Facile synthesis of a sulfur/multiwalled carbon nanotube nanocomposite cathode with core–shell structure for lithium rechargeable batteries

A novel sulfur/multiwalled carbon nanotube nanocomposite (S/MWCNT) was prepared by a facile quasi-emulsion template method in an O/W system. Transmission and scanning electronic microscopy show the formation of a highly developed core–shell tubular structure consisting of S/MWCNT composite with uniform sulfur coating on its surface. The homogenous dispersion and integration of MWCNT in the S/MWCNT composite create a highly conductive and mechanically flexible framework, enhancing the electronic conductivity and consequently the rate capability of the material. The S/MWCNT composite cathode could deliver a stable discharge (the fifth cycle) capacity of about 903 mAh g^?1 at 0.1 C, 751 mAh g^?1 at 0.5 C, and 631 mAh g^?1 at 1 C.     

A novel composite anode for LIB prepared via template-like-directed electrodepositing Cu–Sn alloy process

A novel composite anode material consisted of electrodeposited Cu–Sn alloy dispersing in a conductive micro-porous carbon membrane coated on Cu current collector was investigated. The composite material was prepared by template-like-directed electrodepositing Cu–Sn alloy process and then annealing. The template-like microporous membrane electrode was obtained as follows: (1) casting a polyacrylonitrile (PAN) solution on a copper foil, (2) then immersing the copper foil into deionized water for phase inversion, and (3) drying the membrane electrode. This method provided the composite material with high decentralization of Cu–Sn alloy and supporting medium function of conductive carbon membrane deriving from pyrolysis of PAN. SEM, XRD, and EDS analysis confirmed this structure. The characteristic structure was beneficial to inhibit the aggregation among Cu–Sn microparticles, to relax the volume expansion during cycling, and to improve the cycle ability of electrode. The reversible charge/discharge capacity of the composite material remained more than 426.6 and 445.1 mAh g⁻¹, respectively, after 70 cycles, while that of the electrode prepared by electrodepositing Cu–Sn on a bare Cu foil decreased seriously to only 11.3 mAh g⁻¹. These results show that the novel preparing anode process for LIB is a promising method and can achieve composite materials with larger specific capacity and long cycle life.     

Analysis on diffusion-induced stress for multi-layer spherical core–shell electrodes in Li-ion batteries

Silicon-based carbon composites are believed as promising anodes in the near future due to their outstanding specific capacity and relatively lower volume effect compared to pure silicon anodes. Herein, a multilayer spherical core–shell(MSCS) electrode with a graphite framework prepared with Si@O-MCMB/C nanoparticles is developed, which aims to realize chemically/mechanically stability during the lithiation/delithiation process with high specific capacity. An electrochemical-/mechanical-coupling model for the M-SCS structure is established with various chemical/mechanical boundary conditions.The simulation of finite difference method(FDM) has been conducted based on the proposed coupling model, by which the diffusion-induced stress along both the radial and the circumferential directions is determined. Moreover, factors that influence the diffusion-induced stress of the M-SCS structure have been discussed and analyzed in detail.     

Strong lithium-polysulfide anchoring effect of amorphous carbon for lithium–sulfur batteries

Solving the shuttle effect caused by lithium polysulfide (LPS) dissolution is important in lithium−sulfur batteries. The anchoring of LPSs to carbon combined with sulfur is a method of suppressing the shuttle effect. This first-principles study is the first to report that amorphous carbon offers the best ability to anchor LPSs. The adsorption energies of LPSs on amorphous carbon are at least six times higher than those on graphene and at least two times higher than those on pyridinic-N doped graphene. The LPSs adsorbed on amorphous carbon undergo significant molecular distortion and/or partial dissociation due to the S-to-C electron transfer of 1.2–1.8 e per molecule, as well as the formation of strong bonds between both the Li and S atoms and the sp- and sp²-site C atoms. We propose an amorphous carbon−graphite hybrid anchoring material, because amorphous carbon can strongly capture LPSs and graphite can act as an electron channel.     

Electrochemical characteristics of Li4 − x Cu x Ti5O12 used as anode material for lithium-ion batteries

Cu-doped Li₄Ti₅O₁₂ (Li_4???x Cu _x Ti₅O₁₂) materials were synthesized by solid-state method. Cu-doping does not change the crystal structure of Li₄Ti₅O₁₂ material but increases its lattice constant. The particle size of Li_4???x Cu _x Ti₅O₁₂ powders decreases with increasing Cu-doping level. Cu-doping does not change the specific capacity at low current density, but can improve the cycling stability and the rate capability of Li₄Ti₅O₁₂ significantly. This is mainly attributed to the enhanced electronic and ionic conductivity and the decreased charge transfer resistance, caused by the increased specific surface area of active Li_4???x Cu _x Ti₅O₁₂ powders. The Li_3.8Cu_0.2Ti₅O₁₂ anode material exhibits the best cycling stability and rate capability.     

Microstructural investigations of zirconium oxide—on core–shell structure of carbon nanotubes

Single-walled carbon nanotubes and multi-walled carbon nanotubes/ZrO₂ nanocomposites were obtained by isothermal hydrolyzing and chemical precipitation method for both the carbon nanotubes. The coating was taken place by dispersion of both the carbon nanotubes in ZrOCl₂·8H₂O aqueous solution. However, a highly conformal and uniform monoclinic zirconia coating was deposited on multi-walled carbon nanotubes rather than single-walled carbon nanotubes by this new and simple method. Also, it has been observed that the thickness of the individual carbon nanotube after zirconia coating was increased by isothermal hydrolyzing process rather than traditional chemical precipitation method and it has been confirmed by high-resolution transmission electron microscopy study.     

Surface and interfacial morphologies of PAN-CVI carbon–carbon composite

Scanning electron microscopy (SEM), polarized light microscopy (PLM), and transmission electron microscopy (TEM) techniques have been used to characterize the normal surface and flank surface microstructure of a polyacrylonitrile (PAN)-based carbon fiber reinforced chemical vapor infiltrated (CVI) matrix carbon–carbon composite. Optical and SEM results indicate that the CVI deposit consists of two structures: an isotropic phase is present in the fiber bundle-bundle junctions and a second highly oriented lamellar structure is present in the intrabundle matrix. TEM shows that matrix platelets are highly parallel to the fiber axis and the crystallites of the matrix near the fiber surface exhibit better alignment than those farther away from fibers.     

Novel electrospun PAN�CPVC composite fibrous membranes as polymer electrolytes for polymer lithium-ion batteries

Composite fibrous membranes based on poly(acrylonitrile)(PAN)-poly(vinyl chloride)(PVC) have been prepared by electrospinning. The fibrous membranes are made up of fibers of 850- to 1,300-nm diameters. These fibers are stacked in layers to produce a fully interconnected pore structure. Polymer electrolytes were prepared by immersing the fibrous membranes in 1 M LiClO₄-PC solution for 60 min. The condition of pure PAN polymer electrolytes is jelly, which has poor mechanical performance and cannot be used. But when PVC with a good mechanical stiffener was added to PAN, the condition of composite PAN?CPVC polymer electrolytes becomes free-standing. In addition, the optimum electrochemical properties have been observed for the polymer electrolyte based on PAN?CPVC (8:2, w/w) to show ionic conductivity of 1.05?×?10^?3 S cm^?1 at 25 °C, anodic stability up to 4.9 V versus Li/Li⁺, and a good compatibility with lithium metal resulting in low interfacial resistance. The promising results showed that fibrous PEs based on PAN?CPVC (8:2, w/w) have good mechanical stability and electrochemical properties. This shows a great potential application in polymer lithium-ion batteries.     

Electrochemical behavior of Mg-doped 7LiFePO4–Li3V2(PO4)3 composite cathode material for lithium-ion batteries

Mg-doping effects on the electrochemical property of LiFePO₄–Li₃V₂(PO₄)₃ composite materials, a mutual-doping system, are investigated. X-ray diffraction study indicates that Mg doping decreases the cell volume of LiFePO₄ in the composite. The cyclic voltammograms reveal that the reversibility of the electrode reaction and the diffusion of lithium ion is enhanced by Mg doping. Mg doping also improves the conductivity and rate capacity of 7LiFePO₄–Li₃V₂(PO₄)₃ composite material and decreases the polarization of the electrode reaction. The discharge capacity of the Mg-doped composite was 93 mAh?g^?1 at the current density of 1,500 mA?g^?1, and Mg-doped composite has better discharge performance than the original 7LiFePO₄–Li₃V₂(PO₄)₃ composite at low temperature, too. At ?30 °C, the discharge capacity of Mg-doped LFVP is 89 mAh?g^?1, higher than that of the original composite. Electrochemical impedance spectroscopy study shows that Mg²⁺ doping could enhance the electrochemical activity of 7LiFePO₄–Li₃V₂(PO₄)₃ composite. Mg doping has a positive influence on the electrochemical performance of the LiFePO₄–Li₃V₂(PO₄)₃ composite material.     

Two-dimensional PC_3 as a promising anode material for potassium-ion batteries: First–principles calculations

With the diversified development of the battery industry, potassium-ion batteries(PIBs) have aroused widespread interest due to their safety and high potassium reserves on earth. However, the lack of suitable anode materials limits their development and application to a certain extent. Based on first-principles calculations, we investigate the possibility of using PC_3 monolayer as the anode material for PIBs. PC_3 sheet has excellent electrical properties and meets the prerequisite of anode materials. The storage capacity of potassium is as high as 1200 m Ah·g~(-1), which is better than many other reported potassium-ion anode materials. In addition, the outstanding advantages of PC_3 sheet, such as low diffusion barrier and moderate open-circuit voltage, make it a potential anode candidate for PIBs.     

Synthesis and electrochemical performance of micro-mesoporous carbon-sulfur composite cathode for Li–S batteries

Even though significant improvement has been made in the Li–S battery technology, the poor cycling and rate performance have always limited the further growth. Thus, the development of cost-effective and high performing electrodes is considered to be an important technology for the practical aspect. It is quite logical that the porous electrode systems can improve the electrochemical performance of a given battery system. Here, this study benchmarks a new class of electrodes based on double (micro and meso)porous carbon spheres (MMPCs) prepared by a facile soft template method followed by wet chemical etching. The particle size analysis, performed by scanning electron microscopy, shows that the templating agents, such as sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide(CTAB), have a distinct effect on the size distribution of carbon particles. Different electrochemical characterizations have been carried out to understand the effect of SDS and CTAB on the electrochemical performance of carbon-sulfur nanocomposite electrode. BET analysis shows that the pore size distribution of the carbon spheres prepared by only the soft template method (MPCs) is mainly in the micropore range, which limits the storage and the dispersive capacity. However, the etched samples (MMPCs) showed better electrochemical performance, such as high initial discharge capacity of 921 mAh g^?1(sulfur loading ～77.2%) with 82.7% capacity retention at the end of 150 cycles at 200 mA g^?1 and an impressive rate capability of 1086 mAh g^?1 at a current density of 100 mA g^?1.This improved performance could be attributed to the double porous structure of MMPCs. Such a feasible and facile architecture provides a good strategy to prepare other different materials that require better material dispersion and electrode/electrolyte interactions.     

Electrochemical properties of α-Fe2O3 /MWCNTs as anode materials for lithium-ion batteries

α-Fe₂O₃/MWCNTs composites were prepared by a simple hydrothermal process. The crystalline structure and the electrochemical performance of the as-synthesized samples were investigated. Results show that as anode materials for lithium-ion batteries, the α-Fe₂O₃/MWCNTs exhibit an initial discharge capacity of 1256 ± 5 mAh g⁻¹ and a stable specific discharge capacity of 430 ± 5 mAh g⁻¹ at ambient temperature, for up to 100 cycles with no noticeable capacity fading, while the initial discharge capacity of the bare Fe₂O₃ is 992.3 mAh g⁻¹, and the discharge capacity is 146.6 mAh g⁻¹ after 100 cycles. Moreover, the α-Fe₂O₃/MWCNTs composites also exhibit excellent rate performance.     

A carbon–LiFePO<Subscript>4</Subscript> nanocomposite as high-performance cathode material for lithium-ion batteries

A cathode material of an electrically conducting carbon–LiFePO₄ nanocomposite is synthesized by wet ball milling and spray drying of precursor powders prior to a solid-state reaction. The structural characterization shows that the composite is composed of LiFePO₄ crystals and 4.8 wt.% amorphous carbon. Galvanostatic charge/discharge measurements indicate that the composite exhibits a superior high energy and high cycling stability. This composite delivers a discharge capacity of 159.1 mAh g⁻¹ at 0.1 C, 150.8 mAh g⁻¹ at 1 C, and 140.1 mAh g⁻¹ at 2 C rate. The capacity retention of 99% is achieved after 200 cycles at 2 C. The 18,650 cylindrical batteries are assembled using the composite as cathode materials and demonstrate the capacity of 1,400 mAh and the capacity retention of 97% after 100 cycles at 1 C. These results reveal that the as-prepared LiFePO₄–carbon composite is one of the promising cathode materials for high-performance, advanced lithium-ion batteries directed to the hybrid electric vehicle and pure electric vehicle markets.