Bitter gourd-shaped Ni3V2O8 anode developed by a one-pot metal-organic framework-combustion technique for advanced Li-ion batteries

The present study reports on the one-pot synthesis of Ni₃V₂O₈ (NVO) electrodes by a simple metal organic framework-combustion (MOF-C) technique for anode applications in Li-ion batteries (LIBs). The particle morphology of the prepared NVO is observed to vary as irregular rods, porous bitter gourd and hybrid micro/nano particles depending on the concentration of the framework linker used during synthesis. In specific, the orthorhombic phase and the unique bitter gourd-type secondary structure comprised of agglomerated nanoparticles and porous morphologies is confirmed using powder X-ray diffraction, electron microscopies, X-ray photoelectron spectroscopy and N₂ adsorption–desorption measurements. When tested for lithium batteries as anode, the bitter gourd-type NVO electrode shows an initial discharge capacity of 1362 mA h g⁻¹ and a reversible capacity of 822 mA h g⁻¹ are sustained at a rate of 200 mA g⁻¹ after 100 cycles. Moreover, at 2000 mA g⁻¹, a reversible capacity of 724 mA h g⁻¹ is retained after 500 cycles. Interestingly, the porous bitter gourd-shaped NVO electrode registered significantly high rate performance and reversible specific capacities of 764, 531 and 313 mA h g⁻¹ at high rates of 1, 5 and 10 A g⁻¹, respectively.     

Carbon coated porous tin peroxide/carbon composite electrode for lithium-ion batteries with excellent electrochemical properties

A porous tin peroxide/carbon (SnO₂/C) composite electrode coated with an amorphous carbon layer is prepared using a facile method. In this electrode, spherical graphite particles act as supporter of electrode framework, and the interspace among particles is filled with porous amorphous carbon derived from decomposition of polyvinylidene fluoride and polyacrylonitrile. SnO₂ nanoparticles are uniformly embedded in the porous amorphous carbon matrix. The pores in amorphous carbon matrix are able to buffer the huge volume expansion of SnO₂ during charge/discharge cycling, and the carbon framework can prevent the SnO₂ particles from pulverization and re-aggregation. The carbon coating layer on the outermost surface of electrode can further prevent porous SnO₂/C electrode from contacting with electrolyte directly. As a result, the repeated formation of solid electrolyte interface is avoided and the cycling stability of electrode is improved. The obtained SnO₂/C electrode presents an initial coulombic efficiency of 77.3% and a reversible capacity of 742 mA h g⁻¹ after 130 cycles at a current density of 100 mA g⁻¹. Furthermore, a reversible capacity of 679 mA h g⁻¹ is obtained at 1 A g⁻¹.     

Effect of Fe-doping followed by C+SiO2 hybrid layer coating on Li3V2(PO4)3 cathode material for lithium-ion batteries

A novel Li₃V₂(PO₄)₃ composite modified with Fe-doping followed by C+SiO₂ hybrid layer coating (LVFP/C-Si) is successfully synthesized via an ultrasonic-assisted solid-state method, and characterized by XRD, XPS, TEM, galvanostatic charge/discharge measurements, CV and EIS. This LVFP/C-Si electrode shows a significantly improved electrochemical performance. It presents an initial discharge capacity as high as 170.8 mA h g⁻¹ at 1 C, and even delivers an excellent initial capacity of 153.6 mA h g⁻¹ with capacity retention of 82.3% after 100 cycles at 5 C. The results demonstrate that this novel modification with doping followed by hybrid layer coating is an ideal design to obtain both high capacity and long cycle performance for Li₃V₂(PO₄)₃ and other polyanion cathode materials in lithium ion batteries.     

Reduced graphene oxide anchored with δ-MnO2 nanoscrolls as anode materials for enhanced Li-ion storage

We developed a one-pot in situ synthesis procedure to form nanocomposite of reduced graphene oxide (RGO) sheets anchored with 1D δ-MnO₂ nanoscrolls for Li-ion batteries. The as-prepared products were characterized by X-ray diffraction (XRD), Raman spectra, X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscope (FESEM) and transmission electron microscope (TEM). The electrochemical performance of the δ-MnO₂ nanoscrolls/RGO composite was measured by galvanostatic charge/discharge cycling and electrochemical impedance spectroscopy. The results show that the δ-MnO₂ nanoscrolls/RGO composite displays superior Li-ion battery performance with large reversible capacity and high rate capability. The first discharge and charge capacities are 1520 and 810 mAh g⁻¹, respectively. After 50 cycles, the reversible discharge capacity is still maintained at 528 mAh g⁻¹ at the current density of 100 mAh g⁻¹. The excellent electrochemical performance is attributed to the unique nanostructure of the δ-MnO₂ nanoscrolls/RGO composite, the high capacity of MnO₂ and superior electrical conductivity of RGO.     

Hydrothermal synthesis of spherical Li4Ti5O12 material for a novel durable Li4Ti5O12/LiMn2O4 full lithium ion battery

Pure spherical Li₄Ti₅O₁₂ spinel material is quickly synthesized via an efficient hydrothermal procedure. The obtained Li₄Ti₅O₁₂ particle size is about 0.5 µm. The Li₄Ti₅O₁₂ has an initial discharge capacity of 162.2 mA h g⁻¹ and capacity retention of 97.5% after 100 cycles at a rate of 0.2 C. Then, a 2.5 V and long-lasting Li-ion cell with a LiMn₂O₄ cathode and a Li₄Ti₅O₁₂ anode is developed. Electrochemical measurements of the cell indicate that the Li₄Ti₅O₁₂/LiMn₂O₄ full cell, with a weight ratio of 1.5 between cathode and anode, exhibits excellent electrochemical performance, delivering a reversible capacity of 130 mA h g⁻¹ at room temperature. The full cell also exhibits outstanding electrochemical performances at high temperature, as it has an initial discharge capacity of 109.6 mA h g⁻¹, along with a capacity retention rate of 88.9% after 100 cycles at 55 °C.     

3D NiCo2S4 nanorod arrays as electrode materials for electrochemical energy storage application

It is essential to develop new electrode materials for electrochemical energy storage to meet the increasing energy demands, reduce environmental pollution and develop low-carbon economy. In this work, binder-free NiCo₂S₄ nanorod arrays (NCS NRAs) on nickel foam electrodes are prepared by an easy and low energy-consuming route. The electrodes exhibit superior electrochemical properties both for alkaline and Li-ion batteries. In 3 M KOH electrolyte, the NCS NRAs achieve a specific capacity of 240.5 mA h g⁻¹ at a current density of 0.2 A g⁻¹, and 105.7 mA h g⁻¹ after 1500 cycles at the current density of 5 A g⁻¹ with capacity retention of 87.3%. As the anode for LIBs, it shows a high initial capacity of 1760.7 mA h g⁻¹ at the current density of 100 mA g⁻¹, corresponding coulombic efficiency of 87.6%, and a rate capacity of 945 mA h g⁻¹ when the current density is improved 10 times. Hence, the NiCo₂S₄ nanorod arrays are promised as electrode materials with competitive performance.     

Porous Fe2O3 nanorods anchored on nitrogen-doped graphenes and ultrathin Al2O3 coating by atomic layer deposition for long-lived lithium ion battery anode

Porous iron oxide (Fe₂O₃) nanorods anchored on nitrogen-doped graphene sheets (NGr) were synthesized by a one-step hydrothermal route. After a simple microwave treatment, the iron oxide and graphene composite (NGr-I-M) exhibits excellent electrochemical performances as an anode for lithium ion battery (LIB). A high reversible capacity of 1016 mAh g⁻¹ can be reached at 0.1 A g⁻¹. When NGr-I-M electrode was further coated by 2 ALD cycles of ultrathin Al₂O₃ film, the first cycle Coulombic efficiency (CE), rate performance and cycling stability of the coated electrode can be greatly improved. A stable capacity of 508 mAh g⁻¹ can be achieved at 2 A g⁻¹ for 200 cycles, and an impressive capacity of 249 mAh g⁻¹ at 20 A g⁻¹ can be maintained without capacity fading for 2000 cycles. The excellent electrochemical performance can be attributed to the synergy of porous iron oxide structures, nitrogen-doped graphene framework, and ultrathin Al₂O₃ film coating. These results highlight the importance of a rational design of electrode materials improving ionic and electron transports, and potential of using ALD ultrathin coatings to mitigate capacity fading for ultrafast and long-life battery electrodes.     

Cathode materials based on carbon nanotubes for high-energy-density lithium–sulfur batteries

The rational integration of conductive nanocarbon scaffolds and insulative sulfur is an efficient method to build composite cathodes for high-energy-density lithium–sulfur batteries. The full demonstration of the high-energy-density electrodes is a key issue towards full utilization of sulfur in a lithium–sulfur cell. Herein, carbon nanotubes (CNTs) that possess robust mechanical properties, excellent electrical conductivities, and hierarchical porous structures were employed to fabricate carbon/sulfur composite cathode. A family of electrodes with areal sulfur loading densities ranging from 0.32 to 4.77 mg cm⁻² were fabricated to reveal the relationship between sulfur loading density and their electrochemical behavior. At a low sulfur loading amount of 0.32 mg cm⁻², a high sulfur utilization of 77% can be achieved for the initial discharge capacity of 1288 mAh g_S⁻¹, while the specific capacity based on the whole electrode was quite low as 84 mAh g_{C/S+binder+Al}⁻¹ at 0.2 C. Moderate increase in the areal sulfur loading to 2.02 mg cm⁻² greatly improved the initial discharge capacity based on the whole electrode (280 mAh g_{C/S+binder+Al}⁻¹) without the sacrifice of sulfur utilization. When sulfur loading amount further increased to 3.77 mg cm⁻², a high initial areal discharge capacity of 3.21 mAh cm⁻² (864 mAh g_S⁻¹) was achieved on the composite cathode.     

High performance Na3V2(PO4)3 cathode prepared by a facile solution evaporation method for sodium-ion batteries

Based on its abundance and low cost, sodium based batteries have aroused extensive attention for large scale energy-storage systems. In the current work, Na₃V₂(PO₄)₃ prepared by a facile solution evaporation method (denoted as NVP-SE) is used as cathode materials for sodium ion battery, with a control sample by solid state method. Raman spectrum and TEM are used to study the carbon layer coated on NVP-SE. The results show a highly graphitization and well-coated carbon layer, which is predominant by sp² carbon. Graphitized carbon leads to high electrical conductivity, which can improve the rate performance of Na₃V₂(PO₄)₃ materials. Besides, GITT tests show high Na-ion diffusion coefficient. Even at 30 C, the NVP-SE cathode still delivers a capacity of 70 mAh g⁻¹. Moreover, the material also shows great long term cycling performance. After 500 cycles at 1 C rate and 1000 cycles at 5 C, its discharge capacities are still 103.3 mAh g⁻¹ and 85.4 mAh g⁻¹, which maintain 92.6% and 85.0% of its initial capacity. Thus, simple preparation process and excellent electrochemical performance for Na₃V₂(PO₄)₃/C extend it as a potential material for high power applications.     

Nano-Y2O3-coated LiNi0.5Co0.2Mn0.3O2 cathodes with enhanced electrochemical stability under high cut-off voltage and high temperature

LiNi_0.5Co_0.2Mn_0.3O₂ (523) coated with ~ 20 nm thick Y₂O₃ nano-membrane is prepared via a sol-type chemical precipitation process based on electrostatic attraction between the materials. The nano-Y₂O₃-coated 523 cathode can deliver 160.3 mA h g⁻¹ (87.8% of its initial discharge capacity) after 50 cycles at 1 C (180 mA g⁻¹) between 3.0 and 4.6 V by coin cell testing, while the pristine 523 keeps only 146.2 mA h g⁻¹ with 78.6% capacity retention left. The capacity retention rate increases from 50% to 86.7% after 150 cycles at 1 C in 3.0–4.35 V by soft package testing under 45 °C. Through this novel Y₂O₃ coating operation, both the charge transfer resistance and the electrode polarization of the 523 electrode have been suppressed, and its structure stability is also improved.     

Synthesis of nanosheet-structured Na3V2(PO4)3/C as high-performance cathode material for sodium ion batteries using anthracite as carbon source

Recently, Na₃V₂(PO₄)₃ has shown great promise as cathode material for sodium-ion batteries. In this study, a series of carbon-modified Na₃V₂(PO₄)₃ (NVP/C) composites have been synthesized using anthracite as the carbon source. The NVP/C composite shows a nanosheet shape with a 3D continuously conductive network composed of carbon layer and carbon bump. The effect of anthracite dosage on the electrochemical performance of NVP/C has also been investigated. The results show that the NVP/C composite prepared with 10 wt% anthracite (NVP/C-10) exhibits the highest rate capability and a great cycle stability. Especially the NVP/C-10 electrode behaves an average capacity as high as 97 mAh g⁻¹ at a high current rate of 10 C. Moreover, NVP/C-10 still delivers a high specific capacity of 97.5 mAh g⁻¹ even after 800 cycles at 5 C, showing a very low capacity fading ratio of 0.012% per cycle. The excellent rate capability and cycle stability of NVP/C-10 can be ascribed to the synergistic effects of the nanosheet structure and the 3D continuously conductive network. Our results demonstrate that anthracite can be a promising carbon source for the preparation of NVP/C and other polyanion cathode materials as well.     

Electrochemical characterization of P2-type layered Na2/3Ni1/4Mn3/4O2 cathode in aqueous hybrid sodium/lithium ion electrolyte

P2-type layered Na_2/3Ni_1/4Mn_3/4O₂ has been synthesized by a solid-state method and its electrochemical behavior has been investigated as a potential cathode material in aqueous hybrid sodium/lithium ion electrolyte by adopting activated carbon as the counter electrode. The results indicate that the Na⁺/Li⁺ ratio in aqueous electrolyte has a strong influence on the capacity and cyclic stability of the Na_2/3Ni_1/4Mn_3/4O₂ electrode. Increase on the Li⁺ content leads to a shift of the redox potential towards a high value, which is favorable for the improvement of the working voltage of the layered material as cathode. It is found that the coexistence of Na⁺ and Li⁺ in aqueous electrolyte can improve the cyclic stability for the Na_2/3Ni_1/4Mn_3/4O₂ electrode. A reversible capacity of 54 mAh g⁻¹ was obtained with a high cyclability as the Na⁺/Li⁺ ratio was 2:2. Furthermore, an aqueous hybrid ion cell was assembled with the as-proposed Na_2/3Ni_1/4Mn_3/4O₂ as cathode and NaTi₂(PO₄)₃/graphite synthesized in this work as anode in 1 M Na₂SO₄/Li₂SO₄ (mole ratio as 2:2) mixed electrolyte. The cell shows an average discharge voltage at 1.2 V, delivering an energy density of 36 Wh kg⁻¹ at a power density of 16 W kg⁻¹ based on the total mass of the active materials.     

Synthesis of Mn3O4/N-doped graphene hybrid and its improved electrochemical performance for lithium-ion batteries

Mn₃O₄/N-doped graphene (Mn₃O₄/NG) hybrids were synthesized by a simple one-pot hydrothermal process. The scanning electron microscopy (SEM), transition electron microscopy (TEM), X-ray powder diffraction (XRD), Thermogravimetric analysis (TG), Raman Spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to characterize the microstructure, crystallinity and compositions. It is demonstrated that Mn₃O₄ nanoparticles are high-dispersely anchored onto the individual graphene nanosheets, and also found that, in contrast with pure Mn₃O₄ obtained without graphene added, the introduction of graphene effectively restricts the growth of Mn₃O₄ nanoparticles. Simultaneously, the anchored well-dispersed Mn₃O₄ nanoparticles also play a role as spacers in preventing the restacking of graphene sheets and producing abundant nanoscale porous channels. Hence, it is well anticipated that the accessibility and reactivity of electrolyte molecules with Mn₃O₄/NG electrode are highly improved during the electrochemical process. As the anode material for lithium ion batteries, the Mn₃O₄/NG hybrid electrode displays an outstanding reversible capacity of 1208.4 mAh g⁻¹ after 150 cycles at a current density of 88 mA g⁻¹, even still retained 284 mAh g⁻¹ at a high current density of 4400 mA g⁻¹ after 10 cycles, indicating the superior capacity retention, which is better than those of bare Mn₃O₄, and most other Mn₃O₄/C hybrids in reported literatures. Finally, the superior performance can be ascribed to the uniformly distribution of ultrafine Mn₃O₄ nanoparticles, successful nitrogen doping of graphene and favorable structures of the composites.     

Effect of graphene nanosheets on electrochemical performance of Li4Ti5O12 in lithium-ion capacitors

In order to improve the electrochemical performance of lithium titanium oxide, Li₄Ti₅O₁₂ (LTO), for the use in the lithium-ion capacitors (LICs) application, LTO/graphene composites were synthesized through a solid state reaction. The composite exhibited an interwoven structure with LTO particles dispersed into graphene nanosheets network rather than an agglomerated state pristine LTO particles. It was found that there is an optimum percentage of graphene additives for the formation of pure LTO phase during the solid state synthesis of LTO/graphene composite. The effect of graphene nanosheets addition on electrochemical performance of LTO was investigated by a systemic characterization of galvanostatic cycling in lithium and lithium-ion cell configuration. The optimized composite exhibited a decreased polarization upon cycling and delivered a specific capacity of 173 mA h g⁻¹ at 0.1 C and a well maintained capacity of 65 mA h g⁻¹ even at 20 C. The energy density of 14 Wh kg⁻¹ at a power density of 2700 W kg⁻¹ was exhibited by a LIC full cell with a balanced mass ratio of anode to cathode along with a superior capacitance retention of 97% after 3000 cycles at a current density of 0.4 A g⁻¹. This boost in reversible capacity, rate capability and cycling performance was attributed to a synergistic effect of graphene nanosheets, which provided a short lithium ion diffusion path as well as facile electron conduction channels.     

Aqueous slurry of S-doped carbon nanotubes as conductive additive for lithium ion batteries

S-doped carbon nanotubes (SCNTs) obtained by a post treatment approach are used as conductive additive for LiFePO₄ (LFP) cathodes in Lithium ion batteries (LIBs). The SCNTs exhibit higher specific surface area, higher conductivity and better hydrophily as compared to the pristine CNTs because of S doping. Thus the SCNTs can be stably dispersed in water, forming an aqueous conductive slurry. The LFP cathode using the aqueous SCNTs slurry as conductive additive exhibits excellent electrochemical performances in terms of capacity (143 mA h g⁻¹ at 2 C), rate capability and cycling stability (99.6% of initial capacity after 200 cycles) due to the uniform dispersibility of SCNTs in the bulk of electrodes forming a continuous conductive network. The full cell configuration with graphite as anode, affords a high reversible capability (150 mA h g⁻¹ at 0.2 C), good cycling stability (capacity retention of 87.6% at 2 C), ultrahigh energy density of 163.7 W h kg⁻¹ and power density of 296.8 W kg⁻¹. Our results provide an easy approach to prepare high performance LIB cathodes using water as solvent, thus leading to lower cost and more secure for the electrode production.     

Synthesis and characterization of MnCo2O4 microspheres based air electrode for rechargeable sodium-air batteries

In this work, the nanosized porous MnCo₂O₄ microspheres were synthesized by a hydrothermal method and their electrochemical behaviors were investigated based on a carbon supported composite air electrode for rechargeable sodium-air batteries. Under dry air test condition, the MnCo₂O₄/C air electrode demonstrated a stable working voltage of around 2.1 V vs. Na⁺/Na and a high initial discharge capacity of 7709.4 mA h g⁻¹, based on the active material mass, at a current density of 0.1 mA cm⁻². By a limit on the depth of discharge, the cell exhibited a specific capacity of 1000 mA h g⁻¹ with a high cycling stability up to 130 cycles. The considerable electrocatalytic activity suggests that the as-proposed MnCo₂O₄ is a highly efficient catalyst as air electrode for rechargeable sodium-air batteries.     

Hydrazine hydrate-induced hydrothermal synthesis of MnFe2O4 nanoparticles dispersed on graphene as high-performance anode material for lithium ion batteries

Herein, a MnFe₂O₄/graphene (MnFe₂O₄/G) nanocomposite has been synthesized via a facile N₂H₄·H₂O-induced hydrothermal method. During the synthesis, N₂H₄·H₂O is employed to not only reduce graphene oxide to graphene, but also prevent the oxidation of Mn²⁺ in alkaline aqueous solution, thus ensuring the formation of MnFe₂O₄/G. Moreover, MnFe₂O₄ nanoparticles (5–20 nm) are uniformly anchored on graphene. MnFe₂O₄/G electrode delivers a large reversible capacity of 768 mA h g⁻¹ at 1 A g⁻¹ after 200 cycles and high rate capability of 517 mA h g⁻¹ at 5 A g⁻¹. MnFe₂O₄/G holds great promise as anode material in practical applications due to the outstanding electrochemical performance combined with the facile synthesis strategy.     

Rational design of mesoporous LiFePO4@C nanofibers as cathode materials for energy storage

In this work, the mesoporous LiFePO₄@C nanofibers have been successfully fabricated through a facile electrospinning method. The structure, morphology, chemical composition and lithium storage performance have been systematically investigated. The results reveal that the LiFePO₄ grains with particle size of ～15 nm are uniformly dispersed in the mesoporous carbon nanofibers. The LiFePO₄@C electrode presents a high reversible capacity and excellent rate performance. It delivers a discharge capacity of 107 mAh g⁻¹ and retains 105 mAh g⁻¹ over 200 cycles at 10C. The excellent electrochemical performances are attributed to the novel nanostructure where LiFePO₄ nanoparticles are embedded in the carbon fibers. This designed structure can significantly enhance the conductivity of LiFePO₄@C, accelerate the diffusion of electrolyte, and thus facilitate the transport of electrons and Li-ions.     

Sulfur-doped mesoporous carbon from surfactant-intercalated layered double hydroxide precursor as high-performance anode nanomaterials for both Li-ion and Na-ion batteries

We describe a preparation of sulfur-doped mesoporous amorphous carbon (SMAC) from a commercially available alkyl surfactant sulfonate anion-intercalated NiAl-layered double hydroxide precursor via thermal decomposition and subsequent acid leaching. The resultant amorphous carbon is endowed with the integrated advantage of featuring high reversible capacity and long cycling stability: intrinsic doping of sulfur, large specific area, and broad mesopore size distribution. Electrochemical evaluation shows that the SMAC electrode exhibits highly enhanced electrochemical performances, compared with the electrode of non-doped mesoporous and amorphous carbon prepared by using a different surfactant (sodium laurate). A high reversible capacity of 958 mA h g⁻¹ is achieved for the SMAC electrode after 110 cycles at 200 mA g⁻¹, and especially a superlong cycle life with a reversible capacity of 579 mA h g⁻¹ after 970 cycles at 500 mA g⁻¹. Moreover, the SMAC electrode can facilitate the reversible insertion/extraction of Na ion, owing to the proper specific area and mesopore size distribution, as well as the improved electronic conductivity resulted from doping of sulfur.     

Carbon-coated SiO/ZrO2 composites as anode materials for lithium-ion batteries

A combination of high-energy ball milling and constant pressure chemical vapor deposition was used to prepare carbon-coated SiO/ZrO₂ composites. It was found that the as-prepared composites were composed of amorphous carbon, amorphous SiO, and paracryslalline ZrO₂. The electrochemical analysis results revealed excellent electrochemical performances for the composites, including a high initial discharge capacity (1737 mA h g⁻¹), a remarkable cyclic stability (reversible capacity of 721 mA h g⁻¹ at 800 mA g⁻¹, after 100 cycles), and a good rate capability (870 mA h g⁻¹ at 800 mA g⁻¹). These features demonstrate that these composites are promising alternative candidates for high-efficiency electrode materials of Li-ion batteries.