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.     

Sulfur composite cathode materials: comparative characterization of polyacrylonitrile precursor

The electrochemical behavior of the sulfur composite cathode material for rechargeable lithium batteries and the characteristic of the polyacrylonitrile precursor were investigated. The samples of different polyacrylonitrile precursors were characterized by thermogravimetric analysis, nuclear magnetic response, Fourier transform infrared spectrometer, and differential scanning calorimetry. The electrochemical performance of the sulfur composite cathode material made from the polyacrylonitrile precursor was also tested. The analysis showed that the molecular weight distribution and the impurity of the polyacrylonitrile precursor affected the electrochemical performance of the sulfur composite cathode material made from the precursor. The polyacrylonitrile precursor with the narrower distribution of the molecular weight and the higher structural purity of the polyacrylonitrile precursor led the better electrochemical performance of the sulfur composite cathode material made from the precursor.     

Preparation of MnO<Subscript>2</Subscript>/WMNT composite and MnO<Subscript>2</Subscript>/AB composite by redox deposition method and its comparative study as supercapacitive materials

The manganese oxide/multi-walled carbon nanotube (MnO₂/MWNT) composite and the manganese oxide/acetylene black (MnO₂/AB) composite were prepared by translating potassium permanganate into MnO₂ which formed the above composite with residual carbon material using the redox deposition method and carbon as a reducer. The products were characterized by X-ray diffraction, Fourier transform infrared, and scanning electron microscope. Electrochemical properties of both the MnO₂/MWNT and MnO₂/AB electrodes were studied by using cyclic voltammetry, electrochemical impedance measurement, and galvanostatic charge/discharge tests. The results show that the MnO₂/MWNT electrode has better electrochemical capacitance performance than the MnO₂/AB electrode. The charge–discharge test showed the specific capacitance of 182.3 F·g⁻¹ for the MnO₂/MWNT electrode, and the specific capacitance of 127.2 F·g⁻¹ for the MnO₂/AB electrode had obtained, within potential range of 0–1 V at a charge/discharge current density of 200 mA·g⁻¹ in 0.5 mol·L⁻¹ potassium sulfate electrolyte solution in the first cycle. The specific capacitance of both the MnO₂/MWNT and MnO₂/AB electrodes were 141.2 F·g⁻¹ and 78.5 F·g⁻¹ after 1,200 cycles, respectively. The MnO₂/MWNT electrode has better cycling performance. The effect of different morphologies was investigated for both MnO₂/MWNT and MnO₂/AB composites.     

Charge/discharge characteristics of sulfur composite electrode at different temperature and current density in rechargeable lithium batteries

The charge/discharge characteristics of the sulfur composite cathodes were investigated at different temperatures and different current densities. The composite presented the discharge capacities of 854 and 632 mAh g⁻¹ at 60 and −20 °C, respectively, while it had the discharge capacities of 792 mAh g⁻¹ at 25 °C. The composite presented the discharge capacities of 792 and 604 mAh g⁻¹ at 55.6 and 667 mA g⁻¹, respectively, at room temperature. The results showed that the sulfur composite cathodes presented good charge/discharge characteristics between 60 and −20 °C and at a high c-rate up to 667 mA g⁻¹.     

Performance of solid-state hybrid supercapacitor with LiFePO4/AC composite cathode and Li4Ti5O12 as anode

We report the studies on quasi-solid battery-supercapacitor (BatCap) systems fabricated using sol–gel-prepared LiFePO₄ and its composites (LACs) with activated charcoal (AC) as hybrid cathode and Li₄Ti₅O₁₂ powder as anode separator by flexible gel polymer electrolyte (GPE) film. The GPE film comprises 1.0 M lithium trifluoromethane sulfonate (LiTf) solution in ethylene carbonate (EC)–propylene carbonate (PC) mixture, immobilized poly(vinylidene fluoride-co-hexafluoro-propylene) (PVdF-HFP), which is of high ionic conductivity (∼3.8 × 10⁻³ S cm⁻¹ at 25 °C) and electrochemical stability window (∼3 V). The effect of the addition of AC in composite electrode LACs has been analyzed using various techniques such as X-ray diffraction, porosity analysis, and electrochemical methods. The interfaces of composite LACs and GPE film not only offer high rate performance but also show high specific energy (>27.8 Wh kg⁻¹) as compared to the symmetric supercapacitors and pristine lithium iron phosphate (LiFePO₄)-based lithium ion batteries. The full BatCap systems have been characterized by cyclic voltammetry and galvanostatic charge–discharge tests. The BatCap systems with composite electrodes (LACs) offer better cyclic performance as compared to that of pristine LiFePO₄-based BatCap or LIB LiFePO₄/Li₄Ti₅O₁₂.

     

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.     

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.     

电化学阴极沉积制备氧化钴/CNTs复合电极的准电容特性

采用电化学阴极沉积还原Co(NO3)2的方法制备了具有准电容特性的氧化钴电极材料,其比容量达到280 F／g,采用CNTs作为电极基体,在其表面均匀的沉积了纳米钴化镍颗粒并由此制备了氧化钴碳纳米管复合电极材料.采用循环伏安,恒流充放电,交流阻抗及扫描电镜等方法考察了复合电极材料的容量特性、阻抗特性、自放电特性以及电极表观特征．实验表明复合电极具有良好的电化学特性,CNTs基体在明显降低氧化镍材料的阻抗的同时还提高了电极材料的电化学容量并拓宽了电极材料的有效工作电位窗,复合电极在1 mol／L KOH电解液中比容量达到322 F／g且表现了良好的电化学可逆性．并分别采用氧化钴／CNTs复合电极作为正极,活性炭纤维作为负极制备了复合型电化学电容器,其工作电压达到1．4 V,电容器质量比容量达到47 F／g．在0．1 A／cm2放电时,复合型电容器的能量密度达到10 Wh／kg,兼具高能量特性和优良的大电流放电特性．     

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.     

Impedance studies on bismuth-ruthenate-based electrodes

Doped bismuth ruthenates and bismuth ruthenate-stabilized bismuth oxide composites were studied as prospective cathode material for solid oxide fuel cells. Symmetric cells were fabricated on gadolinium-doped ceria electrolytes and studied by electrochemical impedance spectroscopy. Ca- and Ag-doped bismuth ruthenate electrodes (5–10 mol%) showed the same characteristic frequency as undoped bismuth ruthenate but with higher activation energy and slightly better performance above ∼550 °C. At 700 °C, area-specific resistance (ASR) of undoped, 5 mol% Ca and 5 mol% Sr-doped bismuth ruthenate electrode was 1.45, 1.24, and 1.41  Ωcm², respectively. The change in ASR as a function of oxygen partial pressure and current bias suggests that the rate-limiting steps for oxygen reduction in bismuth ruthenate systems are charge transfer and surface diffusion of dissociatively adsorbed oxygen to triple phase boundaries. Introduction of the erbia-stabilized bismuth oxide (ESB) phase reduced both the rate-limiting steps resulting in much improved electrode performance. At 700 °C, composite electrodes containing 31.25–43.75 wt% ESB exhibited an ASR of 0.08–0.11 Ωcm².     

Cathodic performance of V2O5 nanowires and reduced graphene oxide composites for lithium ion batteries

In this study, vanadium pentoxide (V₂O₅) nanowires (NWs) with a diameter of 100–200 nm and a length of up to several micrometers as cathode for lithium ion batteries are synthesize using an electrospinning method. The reduced graphene oxide (rGO) and V₂O₅ NWs (GVO) composites are form by wet mixing the electrospun V₂O₅ NWs and rGO. Surface morphologies, microstructure and elemental mapping, and chemical bonding states of the composites are characterize. The initial and 60 cycles discharge capacities of GVO composite composed of 1 wt% rGO show up to 225 mAh g⁻¹ and 125 mAh g⁻¹, even higher than pure V₂O₅ NWs, when the lithium ion battery cycled between 2.0 and 4.0 V with a rate of 0.2 C, because of highly conductive rGO. The GVO composite could be promising as a high performance cathode for lithium ion batteries.     

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.     

Electrochemical properties of modified acetylene black/sulfur composite cathode material for lithium/sulfur batteries

Lithium/sulfur (Li/S) batteries have a high theoretical specific capacity of 1672 mAh g^?1. However, the insulation of the elemental sulfur and polysulfides dissolution could result in poor cycling performance of Li/S batteries, thus restricting the industrialization process. Here, we prepared sulfur-based composite by thermal treatment. The modified acetylene black (H-AB) was used as a carrier to fix sulfur. The H-AB could interact with polysulfides and reduce the dissolution of polysulfides in the electrolyte. Nonetheless, the conductivity of H-AB relatively reduced. So the conductivity of the sulfur electrode would be improved by the addition of the conductive agent (AB). In this paper, the different content of conductive agent (AB) in the sulfur electrode was studied. The electrochemical tests indicate that the discharge capacity of the sulfur electrode can be increased by increasing the conductive agent (AB) content. The H-AB@S composite electrode with 30 wt.% conductive agent has the best cycle property. The discharge capacity still remains at 563 mAh g^?1 after 100 cycles at 0.1 C, which is 71% retention of the highest discharge capacity.     

Effects of binder content on manganese dissolution and electrochemical performances of spinel lithium manganese oxide cathodes for lithium ion batteries

In this study, the effects of the polyvinylidene fluoride (PVdF) binder on the Mn dissolution behavior and electrochemical performances of LiMn₂O₄ (LMO) electrodes are investigated. It is found that increasing the PVdF content (3, 5, 7, and 10 wt.%) leads to reduced Mn dissolution, and thus superior cycle performance at elevated temperature (60 °C). This can be ascribed to increased binder coverage on the LMO surface, as evidenced by X-ray photoelectron spectroscopy measurements, which acts a role as a passivation layer for Mn dissolution. The rate capability of the LMO electrode is hardly deteriorated as the PVdF content increases, despite the increasing surface coverage. Electrochemical impedance measurements reveal that the LMO electrode with higher binder loading exhibits lower electrode impedance, which is suggested to be due to enhanced electronic passage through the composite LMO electrode.     

Effects of additives and surface treatment on electrochemical performance for bafeo4 electrode

BaFeO₄ was prepared by using the raw material K₂FeO₄. The structure of the product was characterized by X-ray diffraction and infrared radiation. Particle size and morphology were analyzed by SEM. BaFeO₄, the mixture of BaFeO₄, and additives were used as cathode, zinc used as anode, with which discharge performance test was carried out in the KOH electrolyte with a concentration of 14 mol/L. The results show that the discharge performance of BaFeO₄ is obviously enhanced, the discharge platform is increased by 0.3 V, and the capacity reached up to 240 mAh/g, increased by 40 mAh/g after 5% of K₂S₂O₈ was added. In addition, the discharge capacity is increased by 65 mAh/g via treating the electrode surface with TiO₂ sol, reached up to 265 mAh/g, and electrochemical performance is obviously improved. The reason of improving property is discussed in the work too.     

Low temperature synthesis of layered LiNiO2 cathode material in air atmosphere by ion exchange reaction

The layered LiNiO₂ cathode material for lithium ion battery was synthesized by ion-exchange reaction at low temperature in air atmosphere. The influence of synthesis conditions on the electrochemical performance of the resulting LiNiO₂ was investigated. The LiNiO₂ samples were characterized by X-ray powder diffraction (XRD), scanning electron microscope (SEM) and infrared (IR) analysis. The results indicate that low temperature fabricated LiNiO₂ powders keep a single layered hexagonal structure and homogenous spheric shape like the raw material NiOOH. Charge and discharge tests show that the resultant LiNiO₂ exhibits good electrochemical properties. The first charge and discharge capacities of the sample are 183.4 mA h g^− 1 and 169.5 mA h g^− 1 at 0.5 mA cm^− 2, respectively. Galvanic charge/discharge and cyclic voltammetry tests reflect that LiNiO₂ electrode exhibits good cycle reversibility.     

Electrochemical cell with two layers cathode for NO decomposition

An electrochemical cell composed of an yttria-stabilized zirconia disk and two layers cathode was used for nitrogen monoxide decomposition. It was found that covering the Pt cathode by a mixture of oxygen ionic conductor (YSZ) and electronic conductor (NiO) leads to enhancement of the performance of the electrochemical cell for NO_x decomposition in the presence of excess oxygen. The decomposition activity was measured for the one-compartment cell oxide|(cathode)|YSZ|(anode) by applying a DC voltage lower than 3.7 V in the temperature range 550–700 °C. The microstructure of the YSZ-NiO mixed oxide electrodes was investigated in dependence of the cell operating condition and the working electrode sintering temperature. The correlation between the microstructure of the mixed oxide electrode and conversion rate of NO was studied. The phenomenon of self-optimization of the microstructure of the NiO-YSZ working electrode during the cell operation was observed and investigated. Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Improved of cathode performance of LiFePO<Subscript>4</Subscript>/C composite using different carboxylic acids as carbon sources for lithium-ion batteries

Among the several materials under development for use as a cathodes in lithium-ion batteries olivine-type LiFePO₄ is one of the most promising cathode material. However, its poor conductivity and low lithium-ion diffusion limits its practical application. In this study, we report seven different carboxylic acids used to synthesize LiFePO₄/C composite, and influences of carbon sources on electrochemical performance were intensively studied. The structure and electrochemical properties of the LiFePO₄/C were characterized by X-ray diffraction, scanning electron microscopy, electrical conductivity, and galvanostatic charge–discharge measurements. Among the materials studied, the sample E with tartaric acid as carbon source exhibited the best cell performance with a maximum discharge capacity of 160 mAh g⁻¹ at a 0.1 C-rate. The improved electrochemical properties were attributed to the reduced particle size and enhanced electrical contacts by carbon.     

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.