A novel high specific capacity lithium‐ion capacitor battery with Li+‐doped Ni0.64Al0.64Mn0.56O2 prepared by coprecipitation method as cathode active material

Lithium‐ion capacitor battery is a late‐model energy storage system. It can combine the lithium‐ion battery with the capacitor to ensure that it has a high specific capacity and excellent large‐current discharge performance. In this paper, a novel Li⁺‐doped Ni_0.64Mn_0.64Al_0.56O₂ is synthesized by coprecipitation method and as a capacitor active material with commercialized LiNi_1/3Co_1/3Mn_1/3O₂ in different proportions forms the cathode of the lithium‐ion capacitor batteries. By analyzing the results of physical property characterization, when the mass ratio is 7:3, the crystal size of cathode material is less than 2 μm with uniform porous distribution. And, through electrochemical tests, the cathode has the greatest excellent reversibility, the lowest‐charge resistance, and the fastest‐lithium‐ion diffusion rate. Specific capacity can reach 196.34 mAh g^?1 at 0.5°C and, even at 5°C current density, it also can be 67.63 mAh g^‐1. After 110 times charge and discharge cycles, capacity retention of this cathode material at 5°C still can be over 85%.     

Porous microspheres as additives in lead–acid batteries

The theoretical specific energy of the lead/acid battery is 176 W h kg⁻¹. The specific energy actually achieved depends on the discharge rate but is typically only about 15–25% of this maximum value. The major reason for the lead acid battery's inability to obtain higher specific energies is that much of the active material in both the positive and negative electrode is not discharged. This is especially true at the higher discharge rates where the diffusion of sulfate ions into the positive plate limits the reaction. Porous, hollow, glass microspheres (PHGM) would allow for more electrolyte storage in the electrodes and enhance the high rate energy storage of lead acid batteries. In this paper, we present a method for making hollow, glass microspheres (HGMs) porous. Presently our process only produces small yields. We believe in the future that the yields with our process can be substantially increased. PHGMs could substantially improve the high rate performance of lead acid batteries and make these batteries more attractive for hybrid electric vehicle applications.     

Synergistic effect of sulfur on electrochemical performances of carbon‐coated vanadium pentoxide cathode materials with polyvinyl alcohol as carbon source for lithium‐ion batteries

Vanadium pentoxide (V₂O₅) is a common cathode material for lithium‐ion battery, but its low electronic and ionic conductivity seriously affect its electrochemical performances. In this paper, a type of carbon‐coated V₂O₅ and S composite cathode material with PVA as the carbon source is utilized to lithium‐ion batteries. X‐ray diffraction and Raman test results illustrate that sulfur can make the V₂O₅ lose part of oxygen atoms and become nonstoichiometric vanadium oxide (V₂O_5‐x). Electrochemical test results show that sulfur can provide a considerable proportion of the specific capacity of the whole cathode. This illustrates that the synergistic effect of sulfur can optimize the structure of vanadium pentoxide in order to increase more electron transfer channels, and at the same time, it also can provide additional specific capacity for the whole cathode. When the ratio of V₂O₅ and sulfur is 1:3, the discharge specific capacity can reach 923.02, 688.37, and 592.70 mAh g^?1 at 80, 160, and 320‐mA g^?1 current density, respectively, and after 100 times charge and discharge cycles at 320‐mA g^?1 current density, the capacity retention rate can achieve to more than 60%.     

Jute sticks derived novel graphitic porous carbon nanosheets as Li-ion battery anode material with superior electrochemical properties

Graphitic porous carbon sheets (GPCS), which were synthesized at a low temperature of 900°C by KOH chemical activation technique, possess a specific surface area of 1246 m² g^-1 with high pore volume. The size of the pores varied in micro-mesopore regions and exhibited three-dimensional sheet-like morphology composed of multilayered graphene sheets with an inter planar distance of 0.360 nm. The GPCS material was tested as anode for Li-ion battery (LIB) application in half cell mode (vs Li⁺/Li). The fabricated GPCS electrode shows excellent electrochemical properties in comparison with commercial graphite such as a high discharge specific capacity of 1022 mA h g^-1 after 10 cycles at 100 mA g^-1 and excellent specific capacity retention of 170 mA h g^-1 at a very high current rate of 8000 mA g^-1 and also retains a high capacity of 541 mA h g^-1 after 250 cycles at 500 mA g^-1, which suggests that GPCS material can be a promising electrode for LIB application. A brief comparison with commercial graphite and various carbonaceous materials from literature demonstrated that the GPCS electrode was potential material for high rate LIBs.     

Lignin‐derived heteroatom‐doped porous carbons for supercapacitor and CO2 capture applications

The present study reports the economic and sustainable syntheses of functional porous carbons for supercapacitor and CO₂ capture applications. Lignin, a byproduct of pulp and paper industry, was successfully converted into a series of heteroatom‐doped porous carbons (LHPCs) through a hydrothermal carbonization followed by a chemical activating treatment. The prepared carbons include in the range of 2.5 to 5.6 wt% nitrogen and 54 wt% oxygen in its structure. All the prepared carbons exhibit micro‐ and mesoporous structures with a high surface area in the range of 1788 to 2957 m² g^?1. As‐prepared LHPCs as an active electrode material and CO₂ adsorbents were investigated for supercapacitor and CO₂ capture applications. Lignin‐derived heteroatom‐doped porous carbon 850 shows an outstanding gravimetric specific capacitance of 372 F g^?1 and excellent cyclic stability over 30,000 cycles in 1 M KOH. Lignin‐derived heteroatom‐doped porous carbon 700 displays a remarkable CO₂ capture capacity of up to 4.8 mmol g^?1 (1 bar and 298 K). This study illustrates the effective transformation of a sustainable waste product into a highly functional carbon material for energy storage and CO₂ separation applications.     

Low‐temperature reversible capacity loss and aging mechanism in lithium‐ion batteries for different discharge profiles

In this paper, reversible capacity loss of lithium‐ion batteries that cycled with different discharge profiles (0.5, 1, and 2 C) is investigated at low temperature (?10°C). The results show that the capacity and power degradation is more severe under the condition of low discharge rate, not the widely accepted high discharge rate. To shed some light on the aging phenomena, noninvasive electrochemical methods, ie, incremental capacity and differential voltage analysis, are applied to identify and quantify the effects of different degradation modes (DMs). Apart from the resistance increase, the DMs include the loss of lithium inventory (LLI) and the loss of active material (LAM). Both LLI and LAM decay to a greater extent for the cell cycled with lower discharge rate, and the growth of LAM is higher than that of LLI. Further, the analysis of state of charge (SOC) window shows that the earlier cutoff of the high discharge rate can lead to less mechanical and thermal stress on cathode materials, thus a lower degradation rate. Another cause is that the lithium plating on the anode materials can be mitigated by increasing the charging temperature which results from preceding high rate discharging.     

Flexible graphite as battery anode and current collector

In making graphite-based electrodes and current collectors, there is significant simplification if a flexible graphite process is used. The lithium intercalation capacity of Grafoil^®1 flexible graphite sheet and its powder was evaluated using electrochemical charge–discharge cycling in half-cell configuration (coin cell with Li anode and graphite cathode). The sheet form was used with and without a copper current collector. Excellent electrical conductivity of the monolithic material with very low interface resistance helps as current collector and electrode. The comparatively low capacity of Grafoil^® sheet is thought to be due to diffusion limitation of the structure, especially in the light of the very high capacity of its powder form. The highly irreversible capacity of the powdered material may be due to unfunctionalized graphitic structures or impurities present in the powder. Impedance response for the first intercalation–deintercalation was different than responses taken after several cycles. The presence of a second impedance arc suggests structural modification is taking place in the graphite anode, possibly through formation of a porous structure as a result of graphite expansion.     

Electrospun zeolitic imidazolate framework‐derived nitrogen‐doped carbon nanofibers with high performance for lithium‐sulfur batteries

Three‐dimensional (3D) nitrogen‐doped carbon nanofibers (N‐CNFs) which were originating from nitrogen‐containing zeolitic imidazolate framework‐8 (ZIF‐8) were obtained by a combined electrospinning/carbonization technique. The pores uniformly distributed in N‐CNFs result in the improvement of electrical conductivity, increasing of BET surface area (142.82 m² g^?1), and high porosity. The as‐synthesized 3D free‐standing N‐CNFs membrane was applied as the current collector and binder free containing Li₂S₆ catholyte for lithium‐sulfur batteries. As a novel composite cathode, the free‐standing N‐CNFs/Li₂S₆ membrane shows more stable electrochemical behavior than the CNFs/Li₂S₆ membrane, exhibiting a high first‐cycle discharge specific capacity of 1175 mAh g^?1at 0.1 C and keeping discharge specific capacity of 702 mAh g^?1 at higher rate. More importantly, as the sulfur mass in cathodes was increased at 7.11 mg, the N‐CNFs/Li₂S₆ membrane delivered 467 mAh g^?1after 150 cycles at 0.2 C. The excellent electrochemical properties of N‐CNFs/Li₂S₆ membrane can be ascribed to synergistic effects of high porosity and nitrogen‐doping in N‐CNFs from carbonized ZIF‐8, illustrating collective effects of physisorption and chemisorption for lithium polysulfides in discharge‐charge processes.     

Flexible supercapacitor based on three‐dimensional cellulose/graphite/polyaniline composite

Fast charge‐discharge rate and high areal capacitance, along with high mechanically stability, are the pre‐requisites for flexible supercapacitors to power flexible electronic devices. In this paper, we have used three‐dimensional polyacrylonitrile graphite foam as flexible current collector for electro‐deposition of polyaniline (PANI) nanowires. The graphite foam with PANI was then used to fabricate symmetric supercapacitor. The fabricated supercapacitor in the three‐electrode system shows a high specific capacitance (C_sp) of 357 F.g^?1 and areal capacitance (C_areal) of 7142 mF.cm^?2 in 1 M H₂SO₄ at current density of 80 mA.cm^?2, while using two‐electrode system, it shows C_sp of 256 F.g^?1 and C_areal of 5120 mF.cm^?2 in 1 M H₂SO₄ at current density of 100 mA.cm^?2. The current density of 100 mA.cm^?2 is up to 10 folds higher than reported current densities of many PANI‐based supercapacitors. The high capacitance can be attributed to the spongy network of PANI‐NWs on three‐dimensional graphite surface which provides an easy path for electrolyte ions in active electrode materials. The developed supercapacitor shows specific energy of 64.8 Whkg^?1 and a specific power of 6.1 kWkg^?1 with a marginally decrease of 1.6% in C_sp after 1000^th cycles, along with coulombic efficiency retention of 87% in polyvinyl alcohol/H₂SO₄ gel electrolyte. This flexible supercapacitor exhibits great potential for energy storage application.     

Preparation and properties on the graphite/polypropylene composite bipolar plates with a 304 stainless steel by compression molding for PEM fuel cell

Graphite/polymer composites have high corrosion resistance, low contact resistance and low fabrication cost but low cell efficiency and mechanical strength. This study examined the electrical and mechanical properties of graphite/polypropylene composite bipolar plates. Carbon nanotubes (CNTs) were used to improve the electrical properties of the graphite/PP composites. Although the electrical properties increased when excess conducting filler was added to the composite, the mechanical strength decreased significantly. 304 stainless steel (304 SS) plates with different thicknesses were used as the support material of a graphite/PP composite bipolar plate. The 304 SS-supported graphite/PP composite bipolar plate had an optimum CNTs/graphite/PP composite composition of 1.2, 83 and 17 wt.%, respectively. The flexural strength of the 304 SS-supported graphite/PP composites increased from 35 to 58 MPa with increasing 304 SS thickness from 0.5 to 1 mm. The power density of the graphite bipolar plate and 304 SS-supported graphite/PP composite bipolar plate were 968 and 877 mW cm⁻², respectively. The 304 SS complemented the mechanical strength of the graphite/PP composite bipolar plate as well as the cell efficiency.     

Magnetic tubular carbon nanofibers as anode electrodes for high‐performance lithium‐ion batteries

Novel magnetic tubular carbon nanofibers (MTCFs) are prepared through the combination technique of hypercrosslinking, control extraction, and carbonization. The diameter of MTCFs is mainly concentrated between 90 and 120 nm, and the average tube diameter is about 30 nm. A trace amount of Fe₃O₄ exists inside the MTCFs with a particle size of 3 nm, which is formed by in situ conversion of the catalyst (FeCl₃) for the hypercrosslinking reaction. The MTCFs with high surface area (448.74 m² g^?1) and porous wall are used as anode material for lithium‐ion batteries. The electrochemical properties of MTCFs are compared, and tubular carbon nanofibers (TCFs) prepared by the complete extraction. Electrochemical analysis shows that the introduction of Fe₃O₄ nanoparticles makes MTCFs have higher reversible capacity and better rate performance. MTCFs exhibit high reversible specific capacity of 1011.7 mAh g^?1 after 150 cycles at current density of 100 mA g^?1. Even at high current density of 3000 mA g^?1, a remarkable reversible capacity of 270.0 mAh g^?1 is still delivered. Thus, the novel MTCFs show potential application value in anode material for high‐performance lithium‐ion battery.     

One‐pot synthesis of composite NiO/graphitic carbon flakes with contact glow discharge electrolysis for electrochemical supercapacitors

Thanks to their high power density and degree of reversibility, supercapacitors are electrochemical devices that narrow the gap between secondary batteries and traditional dielectric capacitors in the traditional Ragone plot. However, their use is still hindered by their capability to achieve higher energy density. In this work, we present a one‐pot synthesis procedure of composite graphitic carbon flake‐supported NiO for electrochemical energy storage application. We used cathodic contact glow discharge electrolysis by applying 120 Vdc terminal voltage between a thin Pt wire, slightly submerged in an aqueous solution of NiSO₄(H₂O)₆ + Na₂SO₄, and a large surface area carbon graphite anode. Strong active species generated within the micro‐plasma volume locally reduce the nickel precursors to form NiO materials, while at the anodically polarized graphite rod, the forces holding the graphene layers together are weakened by ion/solvent intercalation producing micrometer‐sized graphitic carbon flakes. The morphological characterization is carried out by electron microscopy, energy dispersive X‐ray spectroscopy, powder X‐ray diffraction, and micro‐Raman spectroscopy. Cyclic voltammetry, constant‐current charge/discharge, and electrochemical impedance spectroscopy in 5 mol l^?1 KOH solution are carried out to evaluate the electrochemical energy storage performance of the material. We show that carbon flake‐supported NiO exhibits the dual combination of electric double‐layer capacitance with faradic behavior, giving 495 F g^?1 specific capacitance at 2 A g^?1 current density. Copyright © 2015 John Wiley & Sons, Ltd.     

Preparation of N‐doped graphene powders by cyclic voltammetry and a potential application of them: Anode materials of Li‐ion batteries

Nowadays, doped graphenes are attracting much interest in the field of Li‐ion batteries since it shows higher specific capacity than widely used graphite. However, synthesis methods of doped graphenes have secondary processes that requires much energy. In this study, in situ synthesis of N‐doped graphene powders by using of cyclic voltammetric method from starting a graphite rod in nitric acid solution has been discussed for the first time in the literature. The N‐including functional groups such as nitro groups, pyrrolic N, and pyridinic N have been selectively prepared as changing scanned potential ranges in cyclic voltammetry. The electrochemical performance as anode material in Li‐ion batteries has also been covered within this study. N‐doped graphene powders have been characterized by electrochemical, spectroscopic, and microscopic methods. According to the X‐ray photoelectron spectroscopy and Raman results, N‐doped graphene powders have approximately 16 to 18 graphene rings in their main structure. The electrochemical analysis of graphene powders synthesized at different potential ranges showed that the highest capacity was obtained 438 mAh/g after 10 cycles by using current density of 50 mA/g at N‐GP4. Furthermore, the sample having higher defect size shows better specific capacity. However, the more stable structure due to oxygen content and less defect size improves the rate capabilities, and thus, the results obtained at high current density indicated that the remaining capacity of N‐GP1 was higher than the others.     

Au/Porous silicon‐based sodium borohydride fuel cells

The Au/Porous silicon structure (Au/PS) was developed as hydrogen fuel cell. The use of a porous silicon filled with hydrochloric acid as a proton‐conducting membrane and thin gold film as a catalyst in Au/PS/Si fuel cell is demonstrated. The devices were fabricated by first creating 10–20 µm thick porous silicon layer by anodization etching in a standard silicon wafer and then depositing the gold catalyst film onto the porous silicon. Using sodium borohydride (NaBH₄) solution as the fuel, generation of the open‐circuit voltage of 0.55 V and the fuel cell peak power density of 13 mW cm⁻² at room temperature was achieved. Moreover production of hydrogen by evolution (out‐diffusion) of hydrogen from solid sodium borohydride during thermal annealing at 30–120°C was investigated. Data on the effective diffusion coefficient of the hydrogen in NaBH₄ were determined from intensity changes of infrared vibration peaks of B–H bond (2280 and 3280 cm⁻¹), as a result of thermal annealing of NaBH₄ samples. The relatively high values of the diffusion coefficient of hydrogen, increasing from 1×10⁻⁶ cm² s⁻¹ to 2×10⁻⁴ cm² s⁻¹ suggest that a thermo‐stimulated evolution process can be used for producing hydrogen from NaBH₄. Copyright © 2010 John Wiley & Sons, Ltd.     

Introducing the energy efficiency map of lithium‐ion batteries

The charge, discharge, and total energy efficiencies of lithium‐ion batteries (LIBs) are formulated based on the irreversible heat generated in LIBs, and the basics of the energy efficiency map of these batteries are established. This map consists of several constant energy efficiency curves in a graph, where the x‐axis is the battery capacity and the y‐axis is the battery charge/discharge rate (C‐rate). In order to introduce the energy efficiency map, the efficiency maps of typical LIB families with graphite/LiCoO₂, graphite/LiFePO₄, and graphite/LiMn₂O₄ anode/cathode are generated and illustrated in this paper. The methods of usage and applications of the developed efficiency map are also described. To show the application of the efficiency map, the effects of fast charging, nominal capacity, and chemistry of typical LIB families on their energy efficiency are studied using the generated maps. It is shown how energy saving can be achieved via energy efficiency maps. Overall, the energy efficiency map is introduced as a useful tool for engineers and researchers to choose LIBs with higher energy efficiency for any targeted applications. The developed map can be also used by energy systems designers to obtain accurate efficiency of LIBs when they incorporate these batteries into their energy systems.     

Graphene‐wrapped poly(2,5‐dihydroxy‐1,4‐benzoquinone‐3,6‐methylene) nanoflowers as low‐cost and high‐performance cathode materials for sodium‐ion batteries

Graphene‐wrapped poly 2,5‐dihydroxy‐1,4‐benzoquinone‐3,6‐methylene (PDBM) nanocomposites with three‐dimensional nanoflower structures have been successfully prepared through the ultrasonic exfoliation and reassembly process in methanol. Compact distribution of graphene into the nanocomposite has established a three‐dimensional conductive network, which contributes to improved properties on discharge capacity and cycle performance. Composite with 20 wt% graphene was proved the best ratio when used in sodium‐ion batteries. Its initial discharge capacity can achieve 210 at 30 mA g^?1. After 100 cycles, the capacity is stable at 121 mAh g^?1. The composite featuring highly conductive channels and multidimensional electron transport pathway is synthesized by an easy ultrasonic way, which may be applied in large scales for sodium‐ion batteries.     

Effect of particle size on lithium intercalation rates in natural graphite

The intercalation rate of Li⁺-ions in flake natural graphite with particle size that ranged from 2 to 40 μm was investigated. The amount of Li⁺-ions that intercalate at different rates was determined from measurement of the reversible capacity during deintercalation in 1 M LiClO₄/1:1 (volume ratio) ethylene carbonate–dimethyl carbonate. The key issues in this study are the role of particle size and fraction of edge sites on the rate of intercalation and deintercalation of Li⁺-ions. At low specific current (15.5 mA/g carbon), the composition of lithiated graphite approaches the theoretical value, x=1 in Li_xC₆, except for the natural graphite with the largest particle size. However, x decreases with an increase in specific current for all particle sizes. This trend suggests that slow solid-state diffusion of Li⁺-ions limits the intercalation capacity in graphite. The flake natural graphite with a particle size of 12 μm may provide the optimum combination of reversible capacity and irreversible capacity loss in the electrolyte and discharge rates used in this study.     

Converting rice husk activated carbon into active material for capacitor using three-dimensional porous current collector

We have successfully applied rice husk activated carbon (RHAC) as an active material for the electric double layer capacitor using a three-dimensional (3D) porous current collector. The capacity and cycle stability were evaluated in a 1.0 mol dm⁻³ tetraethylammonium tetrafluoroborate/propylene carbonate solution in the range of 0-2.5 V. The specific capacity of the RHAC was about 14 mAh g⁻¹ at the 50 mA g⁻¹ discharge rate, corresponding to 19 F g⁻¹ under the present conditions. The RHAC cell using the 3D porous current collector possessed a lower internal resistance and better high-rate discharge properties than the RHAC cell using a conventional aluminum (Al) foil collector. After 5000 cycles of charging and discharging, the RHAC cell with the 3D current collector maintained 95% of its initial capacity, while the capacity of the one with the Al foil collector dropped to only 30%.     

Nitrogen doped secondary particle graphite anode for high capacity and high rate Li ion battery

本研究采用低成本易量产的方法制备了二次粒子黏接的石墨负极材料,并对其进行了氮掺杂,制备出具备高比容量和高倍率特性的锂离子电池负极材料。在扣式电池测试中,该材料表现出359.8 mA·h/g的可逆容量,组装的软包装全电池最小比能量可达230 W·h/kg,体积能量密度可达650 W·h/L。该软包装电池具备良好的3 C快速充电能力,充电容量可以在10 min内达到额定容量的51%,30 min即可充满电量,表现出极好的快速充电特性。在室温下进行3 C倍率充电和1 C倍率放电的循环测试中,循环1000次循环后容量保持率依然超过88%的初始容量,循环厚度膨胀率为10.1%,可满足大多数电子设备和电动汽车的需求。     

Aluminate cement/graphite conductive composite bipolar plate for proton exchange membrane fuel cells

Aluminate cement/graphite conductive composite bipolar plate for proton exchange membrane fuel cells (PEMFC) was prepared by mold pressing at room temperature. The effect of size of graphite particles on the conductivity and the flexural strength of composite bipolar plate were discussed. Resistance to acid corrosion, thermal property and pore size distribution of this composite bipolar plate were also investigated in this paper. The experiment results show that the conductivity and the flexural strength of this composite bipolar plate can be improved by choosing uniform size graphite as conductive fillers. The corrosion current is about 10^−4.5 A cm⁻² from polarization curves of this composite bipolar plate, which shows that this composite bipolar plate is acid corrosion-resistant. Al and Ca ions may leach from this composite bipolar plate after 1 M H₂SO₄ acid corrosion. But Al and Ca ions leaching from this composite bipolar plate are only a little percentage of the total Al and Ca ions content in the composite bipolar plate after acid corrosion at 30 °C. This composite bipolar plate is also thermally stable from room temperature to 400 °C. The large amount of pore in this composite bipolar plate is gel capillary pores because of the hydration and solidification of aluminate cement, which make it possess humidifying function during the PEMFC operating.