The electrochemical characteristics of sulfur composite cathode

The electrochemical characteristics of the sulfur composite cathode for reversible lithium storage were investigated based on different charge/discharge manner. The sulfur composites showed novel electrochemical characteristics as well as the high specific capacity and the good cycleability. The investigation showed that the deep discharge down to less than 1.0 V benefited the performance of the sulfur composite cathode, and the overcharge up to 4.0 V deteriorated its performance. The compaction of the sulfur composite electrode was also investigated. The electrochemical performance of the sulfur composite electrodes was tested at the compaction strength from 0 to 24 MPa, showing that the sulfur composites electrode presented the best electrochemical characteristics at the certain compaction strength of 8 MPa. Its performance seriously deteriorated at the compaction strength of 24 MPa. The study reveals that the appropriate compaction strength benefits the electrochemical performance of the sulfur composite electrode.     

Nanoporous carbon microspheres as matrix of sulfur to prepare sulfur/carbon cathode material for lithium–sulfur battery

A high specific surface area (2798.8 m² g^?1) of nanoporous carbon microsphere (NPCM) is prepared by activated carbon microsphere in hot CO₂ atmosphere, which is used as matrix material of sulfur to prepare NPCM/sulfur composite cathode material by a melt-diffusion method. The NPCM/sulfur composite cathode material with the sulfur content of 53.5% shows high discharge capacity; the initial discharge capacity is 1274 mAh g^?1 which maintains as high as 776.4 mAh g^?1 after 50 cycles at 0.1 C current. At high current density of 1 C, the NPCM/sulfur cathode material still shows initial discharge capacity of 830.3 mAh g^?1, and the reversible capacity retention is 78% after 50 cycles. To study the influence of different sulfur content of NPCM/sulfur cathode material to the performance of Li–S battery, the different sulfur content of NPCM/sulfur composite cathode materials is prepared by changing the thermal diffusion time and the ratio of sulfur powder to NPCM. The performance of NPCM/sulfur cathode material with different sulfur content is studied at a current of 0.1 C, which will be very important to the preparation of high-performance sulfur/carbon cathode material with appropriate sulfur content.     

Preparation and evaluation of mechanochemically fabricated LSM/ScSZ composite materials for SOFC cathodes

The LSM/ScSZ composite powder materials for SOFC cathodes were prepared by the mechanical method using an attrition-type particle composing machine and their electrochemical performance was examined. They are designed in such a way that relatively large LSM particles are coated with fine-grained ScSZ particles prior to the electrode fabrication process such as sintering, thus ensuring the establishment of both the ionic and electronic conducting paths within the electrode. The composite cathode using these composite powders outperformed, in the interfacial area specific resistance, a simple LSM cathode and the LSM/ScSZ composite cathode fabricated by an ordinary starting powder mixture without mechanical treatment. The interfacial area specific resistance was actually reduced by 75% relative to the simple LSM cathode, and by 50% relative to the ordinary composite cathode. In addition, the amount of ScSZ doping was reduced down to 20% by weight fraction. The present result suggests that the proposed composite particles can be considered as a potential cathode material in order to enhance SOFC cathode performance.     

Sulfur grown around carbon nanotubes as a cathode material for Li/S battery

Sulfur/multi-walled carbon nanotubes (MWCNTs) composites have been successfully prepared by an in situ growth strategy as a cathode material for lithium/sulfur battery. The microstructure and morphology of the sulfur/MWCNTs composites are characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). From the results, it is found that the nano-sulfur (shell) grows around the MWCNTs (core) and is well-dispersed over the whole surface of the MWCNTs. Tested by coin type cells, the composite materials exhibited the sulfur utilization approaching to 78% for the first cycle, the capacity retention closing to 84% after 100 cycles at various rates. The excellent electrochemical performance could be attributed to the nano-size sulfur and the homogeneous distribution of sulfur on MWCNTs matrix, resulting from this novel in situ growth method, which not only enhances the reactive activity of sulfur during charge–discharge processes but also provides stable electrical and ionic transfer channels.     

Electrochemical characteristics of sulfur composite cathode for reversible lithium storage

The electrochemical characteristics of the sulfur composite cathode for reversible lithium storage were investigated. The sulfur composites showed novel electrochemical characteristics as well as high specific capacity and good cycleability. The sulfur composite presented the average discharge voltage of 1.9 V, which was just the half of conventional LiCoO₂ cathode materials, indicating that the double cells in series presented the same working voltage as conventional LiCoO₂ cells and meaning that the sulfur composite cells will have good interchangeability with conventional LiCoO₂ cells. The overcharge test showed that the sulfur composite cell cannot be charged over 5.0 V, indicating that the sulfur composite cell presented the intrinsic safety for overcharge. Overcharge can cause serious problems for the conventional Li ion cells. The overcharge test also showed that the sulfur composite cell was destroyed when the cell was charged over 4.0 V, resulting in that the cell cannot normally be discharged again. It is found, however, that the sulfur composite cell can be discharged again at very low current density of a 0.002-C rate after the cell was overcharged. Being much safer than lithium metal anode, the graphite anode was used to fabricate sulfur composite/graphite lithium ion cells with a prelithiated sulfur composite cathode, which was produced by electrochemical lithiation. The charge/discharge and cycling characteristics of the sulfur composite/graphite cell was investigated. The result showed that the sulfur composite/graphite cells can be normally cycled and showed the different voltages from that of the cell with the lithium metal anode. This paves the effective way to fabricate safer sulfur composite/graphite lithium ion cells.     

Sulfur/microporous carbon composites for Li-S battery

A commercial carbon black with microporous framework is used as carbon matrix to prepare sulfur/microporous carbon (S/MC) composites for the cathode of lithium sulfur (Li-S) battery. The S/MC composites with 50, 60, and 72 wt.% sulfur loading are prepared by a facile heat treatment method. Electrochemical performance of the as-prepared S/MC composites are measured by galvanostatic charge/discharge tests, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS), with carbonate-based electrolyte of 1.0 M LiPF₆/(PC-EC-DEC). The composite with 50 wt.% sulfur presents the optimized electrochemical performance, including the utilization of active sulfur, discharge capacity, and cycling stability. At the current density of 50 mA g^?1, it can demonstrate a high initial discharge capacity of 1624.5 mAh g^?1. Even at the current density of 800 mA g^?1, the initial capacity of 1288.6 mAh g^?1 can be obtained, and the capacity can still maintain at 522.8 mAh g^?1 after 180 cycles. The remarkably improved electrochemical performance of the S/MC composite with 50 wt.% sulfur are attributed to the carbon matrix with microporous structure, which can effectively enhance the electrical conductivity of the sulfur cathode, suppress the loss of active material during charge/discharge processes, and restrain the migration of polysulfide ions to the lithium anode.     

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.     

Effect of mesoporous carbon containing binary conductive additives in lithium ion batteries on the electrochemical performance of the LiCoO2 composite cathodes

Binary conductive additives (BCA), formed by sonication of mesoporous carbon (MC) and acetylene black (AB), were used as conductive additives to improve the electrochemical performance of a LiCoO₂ composite cathode. The electrochemical performance of the LiCoO₂ composite cathode dispersed with BCA was investigated. The results showed that the electrochemical performance (including the discharge capacity, the discharge voltage and the total internal resistance) of a BCA loaded LiCoO₂ composite cathode was better than that of a cathode loaded with AB. The possible mechanism is that the MC in BCA can adsorb and retain electrolyte solution, which allows an intimate contact between the lithium ions and the cathode active material LiCoO₂ due to its large mesopore specific surface area. A simplified model was also proposed.     

Hydrothermal synthesis of FeS2 for lithium batteries

Nanocrystalline FeS₂ cathode material of lithium cell was synthesized from cheap materials of FeSO₄, Na₂S₂O₃, and sulfur by a hydrothermal process. The scanning electron microscopy analysis showed the obtained material was nano-sized, about 500 nm. The X-ray powder diffraction analysis showed that the synthetic FeS₂ material had two phases of the crystalline structure, pyrite and marcasite. The phase of marcasite seems to have no negative effect on the electrochemical performance of the material. The synthetic FeS₂ showed a significant improvement of electrochemical performance for Li/FeS₂ cells.     

TiN synergetic with micro-/mesoporous carbon for enhanced performance lithium–sulfur batteries

Porous carbon has high specific area and total pore volume but weak interaction with dissolved polysulfides. Conductive polar metal compound has strong chemical adsorption of polysulfides but difficult to attain high porosity to encapsulate sulfur series. Instead of efforts on the cathode, we prepared a composite made up of titanium nitride and three-dimensional micro-/mesoporous carbon by a facile and economic way. This composite was coated on the commercial Celgard separator as a polysulfide interceptor to enhance the performances of lithium–sulfur battery. The strategy exerts the synergetic merits of porosity, chemical adsorption, physical interception, and benign conductivity. The hierarchical carbon possesses a high specific surface area of 1571 m²/g and total pore volume of 1.56 cm³/g with the pore size centered at 1.27 and 5.30 nm. TiN can immobilize sulfur intermediates by strong chemical interaction. In addition, excellent electrical conductivity of TiN facilitates redox kinetics. The pure sulfur cathode with the modified separator delivers high initial capacity of 1130 mAh/g at 1 C (1 C?=?1675 mAh/g) and retains 500 mAh/g after 400 cycles, demonstrating superior cycling stability, rate capabilities. Discharge-charge profiles, electrochemical impedance spectrum, and cyclic voltammetry curves of batteries were investigated to support the prominent electrochemistry of the material. Further analysis and observation on the modified separator disassembled from the coin cells after cycling were conducted to probe the evolution and reaction mechanism of the coating.     

A novel carbon source coated on C-LiFePO<Subscript>4</Subscript> as a cathode material for lithium-ion batteries

The poor electronic conductivity and low lithium-ion diffusion are the two major obstacles to the largely commercial application of LiFePO₄ cathode material in power batteries. In order to improve the defects of LiFePO₄, a novel carbon source polyacrylonitrile (PAN), which would form the hierarchical porous structure after carbonization, is fabricated and used. This work comes up with a simple and facile carbothermal reduction method to prepare porous-carbon-coated LiFePO₄ (C-LiFePO₄-PC) composite and to study the effect of carbon-coated temperature on ameliorating the electrochemical performance. The obtained C-LiFePO₄-PC composite shows a high initial discharge capacity of 164.1 mA h g^?1 at 0.1 C and good cycling stability as well as excellent rate capacity (49.0 mA h g^?1 at 50 C). The most possible factors that improve the electrochemical performance could be related to the enhancement of electronic conductivity and the existence of porous carbon layers. In a word, the C-LiFePO₄-PC material would become an excellent candidate for application in the fields of lithium-ion batteries.     

Phosphazene groups modified sulfur composites as active cathode materials for rechargeable lithium/sulfur batteries

A novel phosphazene groups modified sulfur composites cathode [triphosphazene sulfide composite (PS) or nitroaniline–triphosphazene disulfide composite (NPS)] which can give good affinity with electrolytes was prepared. Their chemical structures were identified by FTIR and XRD analysis. SEM analysis showed PS and NPS had a denser and rougher surface structure than elemental sulfur, with many tiny pores on the surface. Contact angles measurement showed that PS had a hydrophilic surface, which exhibited better affinity of ether solvent. When used as a cathode material in lithium–sulfur batteries, its initial discharge capacity was 1,109 mAh/g for NPS, 784 mAh/g for PS. Discharge capacity of NPS was higher than charge capacity, which implied nitroanilino base on sulfur particles involving in generation of polysulfides.     

Enhanced electrochemical performance of sulfur/polyacrylonitrile composite by carbon coating for lithium/sulfur batteries

A carbon-coated sulfur/polyacrylonitrile (C@S/PAN) core-shell structured composite is successfully prepared via a novel solution processing method. The sulfur/polyacrylonitrile (S/PAN) core particle has a diameter of ~ 100 nm, whereas the carbon shell is about 2 nm thick. The as-prepared C@S/PAN composite shows outstanding electrochemical performance in lithium/sulfur (Li/S) batteries delivering a high initial discharge capacity of 1416 mAh g^?1. Furthermore, it exhibits ~ 89% retention of the initial reversible capacity over 200 cycles at a constant current rate of 0.1 C. The improved performance contributed by the unique composition and the core-shell structure, wherein carbon matrix can also withstand the volume change of sulfur during the process of charging and discharging as well as provide channels for electron transport. In addition, polyacrylonitrile (PAN) matrix suppresses the shuttle effect by the covalent bonding between sulfur (S) and carbon (C) in the PAN matrix.

Open image in new window

Graphical abstract Cycling performance of the S/PAN and C@S/PAN electrodes and TEM image of the C@S/PAN composite.

     

Synthesis and elevated temperature performance of a polypyrrole-sulfur-multi-walled carbon nanotube composite cathode for lithium sulfur batteries

A sulfur-multi-walled carbon nanotube composite (S/MWCNT) was prepared using a two-step procedure of liquid-phase infiltration and melt diffusion. Polypyrrole (PPy) conductive polymer was coated on the surface of the as-prepared S/MWCNT composite by in situ polymerization of pyrrole monomer to obtain PPy/S/MWCNT composite. The composite materials were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The electrochemical performance of the as-prepared cathode material was investigated at 25, 40, and 70 °C at various rates. It was found that temperature has dual effects on the performance of Li/S cells. Increasing the temperature, on one hand, facilitates the lithium ion transport through the cathode and, on the other hand, leads to faster dissolution of active material into the electrolyte. The PPy coating can effectively trap polysulfides in its porous structure, even at elevated temperatures, leading to the improvement of the discharge capacity, the cycle stability, and the coulombic efficiency. The electrochemical impedance spectroscopy (EIS) results reveal that the PPy coating reduces the formation of passive layer on the cathode surface, even at high temperatures, resulting in a better elevated temperature performance. A high reversible capacity of 945 mAh g^?1 was maintained after 50 cycles for the PPy/S/MWCNT composite at 70 °C at a rate of 0.5 C.     

Silver-coated LiVPO4F composite with improved electrochemical performance as cathode material for lithium-ion batteries

Nano-structured LiVPO₄F/Ag composite cathode material has been successfully synthesized via a sol–gel route. The structural and physical properties, as well as the electrochemical performance of the material are compared with those of the pristine LiVPO₄F. X-ray diffraction (XRD) and scanning electron microscopy (SEM) reveal that Ag particles are uniformly dispersed on the surface of LiVPO₄F without destroying the crystal structure of the bulk material. An analysis of the electrochemical measurements show that the Ag-modified LiVPO₄F material exhibits high discharge capacity, good cycle performance (108.5 mAh g⁻¹ after 50th cycles at 0.1 C, 93% of initial discharge capacity) and excellent rate behavior (81.8 mAh g⁻¹ for initial discharge capacity at 5 C). The electrochemical impedance spectroscopy (EIS) results reveal that the adding of Ag decreases the charge-transfer resistance (R_ct) of LiVPO₄F cathode. This study demonstrates that Ag-coating is a promising way to improve the electrochemical performance of the pristine LiVPO₄F for lithium-ion batteries cathode material.     

Enhanced rate performance of polypyrrole-coated sulfur/MWCNT cathode material: a kinetic study by electrochemical impedance spectroscopy

Lithium-sulfur batteries have a poor cyclability and inferior rate capability due to the shuttle effect of lithium polysulfides. To solve these problems, a sulfur-coated MWCNT composite (S/MWCNT) was coated with conductive polypyrrole (PPy) to trap the polysulfides and facilitate charge and lithium ion transport. From the contact angle measurement, it is found that the PPy coating improves the wettability of the S/MWCNT composite. Compared with the bare S/MWCNT composite, the PPy-coated S/MWCNT composite cathode exhibited improved cycle stability and high-rate performance. A reversible discharge capacity of 671 mAh g^?1 was maintained after 50 cycles at 3 C for the PPy-coated composite. The effect of PPy coating on kinetic property was investigated by electrochemical impedance spectroscopy (EIS). The electrolyte resistance, surface film resistance, charge transfer resistance, lithium ion diffusion coefficient, and exchange current density were evaluated from the EIS measurements. The EIS results reveal that the PPy coating increases both Li ion diffusion into the cathode and exchange current density. The as-prepared PPy-coated S/MWCNT composite can be considered to be a promising candidate for high capacity and high-rate performance cathode material.     

Effect of pyrolytic polyacrylonitrile on electrochemical performance of Si/graphite composite anode for lithium-ion batteries

The silicon/graphite (Si/G) composite was prepared using pyrolytic polyacrylonitrile (PAN) as carbon precursor, which is a nitrogen-doped carbon that provides efficient pathway for electron transfer. The combination of flake graphite and pyrolytic carbon layer accommodates the large volume expansion of Si during discharge-charge process. The Si/G composite was synthesized via cost-effective liquid solidification followed by carbonization process. The effect of PAN content on electrochemical performance of composites was investigated. The composite containing 40 wt% PAN exhibits a relatively better rate capability and cycle performance than others. It exhibits initial reversible specific capacity of 793.6 mAh g^?1 at a current density of 100 mA g^?1. High capacity of 661 mAh g^?1 can be reached after 50 cycles at current density of 500 mA g^?1.     

Three-dimensional carbon fiber as current collector for lithium/sulfur batteries

Ni foam and carbon fiber cloth were tested as three-dimensional (3D) current collectors for a sulfur/polypyrrole composite cathode in lithium batteries. The cell with the carbon fiber current collector has exhibited remarkably enhanced electrochemical performance compared with its Ni foam counterpart, delivering a high initial capacity of 1,278 mAh g^?1 and maintaining a discharge capacity at 810 mAh g^?1 after 40 cycles at 0.06 C. Furthermore, the carbon fiber-based cell demonstrated a better rate capability and delivered a highly reversible discharge capacity of 397 mAh g^?1 after 50 cycles at 0.5 C, representing an increase of 194 mAh g^?1 compared to the Ni foam counterpart. The electrochemical property investigations along with scanning electron microscope studies have revealed that the carbon fiber current collector possesses a three-dimensional network structure, provides an effective electron conduction path, and minimizes the loss of electrical contact within the deposited cathode material during cycling. These results indicate that the carbon fiber cloth can be used as a promising, effective, and inexpensive current collector for Li/S batteries.     

A novel binder-sulfonated polystyrene for the sulfur cathode of Li-S batteries

In order to suppress the capacity fading of lithium-sulfur batteries, sulfonated polystyrene (SPS) which was prepared via homogeneous reaction has been applied as a functional binder for the sulfur cathode of lithium sulfur batteries in this study. The SPS and its application for lithium sulfur batteries were characterized by Fourier transformation infrared spectroscopy (FT-IR), thermogravimetry (TG), X-ray diffraction (XRD), scanning electron microscopy (SEM), and charge-discharge test. The traditional binder poly vinylidene fluoride (PVDF) was used for comparison. Results show that for the sulfur cathode with PVDF as binder, the capacity retention after 100 cycles at 200 mA g^?1 is 46.9% and sever voltage fading performance from 10th to 100th cycle can be observed. While for SPS binder, the capacity retention after 100 cycles is 74.4% and there is almost no change of the first plateau at around 2.3 V in the discharge curve from 10th to 100th cycle, indicating obvious electrochemical performance improvement of lithium sulfur battery.     

Three-dimensional nitrogen-doped graphene/sulfur composite for lithium-sulfur battery

A three-dimensional nitrogen-doped graphene/sulfur composite (NGS3) was synthesized by a simple hydrothermal method using urea as the nitrogen source and subsequent thermal treatment. The structure and electrochemical performance of the prepared nitrogen-doped graphene/sulfur composite (NGS3) were confirmed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), Energy dispersive spectroscopy mapping (EDS), and galvanostatic charge/discharge measurements. SEM and EDS mapping show that NGS3 exhibits a porous structure with uniform distribution of sulfur. Compared with the graphene/sulfur composite (NGS1), NGS3 delivers an outstanding rate capability with 1501, 1278, 1136, and 1024 mAh g^?1 at 200, 400, 800, and 1000 mA g^?1, respectively, and the cycle stability of NGS3 is also wonderful, a reversible discharge capacity of 1330 mAh g^?1 is obtained after 80 cycles under the current rate of 200 mA g^?1. The wonderful electrochemical performance could be attributed to the special three-dimensional conductive structure with the help of nitrogen atom.