Unique cyclic performance of post-treated carbide-derived carbon as an anode electrode

Carbide-derived carbon (CDC) is an attractive anode material for Li-ion battery applications because diverse pore textures and structures from amorphous to highly ordered graphite can be controlled by changing the synthesis conditions and precursor, respectively. To elucidate the unique cycling behavior of the post air-treated CDC anode, electrochemical performance was studied under variation of C-rates with structural changes before and after cycling. By tailoring the pore texture of CDCs as removal of amorphous phase by post air-activation, the anode electrode showed a high increase of capacity under prolonged cycling and under high C-rate conditions such as 0.3–1.0 C-rates. The discharge capacities of the treated CDC increased from 400 mAh g⁻¹ to 913 mAh g⁻¹ with increasing cycle number and were close to high initial irreversible value, 1250 mAh g⁻¹, at the 220th cycle under a 0.1C-rate condition, which are unique and unusual cyclic properties in carbon anode applications. Under high C-rate conditions, the discharge capacities started to increase from around 160 mAh g⁻¹ and values of 415 mAh g⁻¹, 372 mAh g⁻¹, and 336 mAh g⁻¹, were observed at 0.3, 0.5, and 1.0 C-rates, respectively, at 600 cycles, demonstrating stable capacity performance.     

Three-dimensional MnO/reduced graphite oxide composite films as anode materials for high performance lithium-ion batteries

MnO/reduced graphite oxide (MnO/RGO) composite films with three dimensionally porous structures have been synthesized by an improved electrostatic spray deposition setup and their microstructure and electrochemical properties have been characterized by X-ray diffraction, scanning electron microscopy, thermal gravimetric, Raman spectrometry and galvanostatic cell cycling. The results show that the structure and electrochemical performance of the electrode film are influenced significantly by the RGO content. The three dimensionally porous structure collapse does not occur in the MnO/RGO thin films for a RGO content lower than 16.58 wt%, the 16.58 wt% reduced graphite oxide content being optimal. Such an improvement in the cycling performance (772 mAh g⁻¹ after 100 cycles at 1 C) and rate capability (425 mAh g⁻¹ at 6 C) might be attributed to the excellent microstructure and electrical conductivity of MnO/reduced graphite oxide composite film electrodes.     

Reduced graphene oxide with superior cycling stability and rate capability for sodium storage

Sodium ion battery is a promising electrical energy storage system for sustainable energy storage applications due to the abundance of sodium resources and their low cost. In this communication, the electrochemical properties of sodium ion storage in reduced graphene oxide (RGO) were studied in an electrolyte consisting of 1 M NaClO₄ in propylene carbonate (PC). The experimental results show that the RGO anode allowed significant sodium ion insertion, leading to higher capacity at high current density compared to the previously reported results for carbon materials. This is due to the fact that RGO possesses higher electrical conductivity and is a more active host, with large interlayer distances and a disordered structure, enabling it to store a higher amount of Na ions. RGO anode exhibits high capacity combined with long-term cycling stability at high current densities, leading to reversible capacity as high as 174.3 mAh g⁻¹ at 0.2 C (40 mA g⁻¹), and even 93.3 mAh g⁻¹ at 1 C (200 mA g⁻¹) after 250 cycles. Furthermore, RGO could yield a high capacity of 141 mAh g⁻¹ at 0.2 C (40 mA g⁻¹) over 1000 cycles.     

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.     

NiCo2O4 nanosheets and nanocones as additive-free anodes for high-performance Li-ion batteries

Development of novel electrode materials with high energy and power densities for lithium-ion batteries (LIBs) is the key to meet the demands of electric vehicles. Transition metal oxides that can react with large amounts of Li⁺ for electrochemical energy storage are considered promising anode materials for LIBs. In this work, NiCo₂O₄ nanosheets and nanocones on Ni foam have been synthesized via general hydrothermal growth and low-temperature annealing treatment. They exhibit high rate capacities and good cyclic performance as LIB anodes owing to their architecture design, which reduces ion and electron transport distance, expands the electrode–electrolyte contact, increases the structural stability, and buffers volume change during cycles. Notably, NiCo₂O₄ nanosheets deliver an initial capacity of 2239 mAh g⁻¹ and a rate capacity of 964 mAh g⁻¹ at current densities of 100 and 5000 mA g⁻¹, respectively. The corresponding values of nanocones are 1912 and 714 mAh g⁻¹. Hence, the as-synthesized NiCo₂O₄ nanosheets and nanocones, which are carbon-free and binder-free with higher energy densities and stronger connections between active materials and current collectors for better stability, are promising for use in advanced anodes for high-performance LIBs.     

Nitrogen-doped carbon-coated hierarchical Li4Ti5O12-TiO2 hybrid microspheres as excellent high rate anode of Li-ion battery

Nitrogen-doped carbon-coated Li₄Ti₅O₁₂-TiO₂ (LTO-TO) hybrid microspheres were prepared by heat treating the dry mixture of urea and chemically lithiated dandelion-like TiO₂ microspheres in a stainless steel autoclave at 550 °C for 5 h. The hybrid materials were tested as anode of Li-ion batteries. As compared to the pristine sample, the N-doped carbon-coated LTO-TO microspheres exhibited higher specific capacity at both low and high current rates. Discharge capacities of 184 and 123 mAh g⁻¹ were obtained at 0.2 C and 20 C, respectively. Moreover, the LTO-TO/C electrode showed excellent cycle performance, with a discharge capacity of 121.3 mAh g⁻¹ remained after 300 cycles at 5 C, corresponding to an average capacity degradation rate of 0.073% per cycle. These high specific capacity, excellent rate capability and cycle performance demonstrated the high potentiality of the N-doped carbon-coated LTO-TO microspheres as anode material of both energy storage-type and power-type Li-ion batteries.     

Amorphous CoS nanoparticle/reduced graphene oxide composite as high-performance anode material for sodium-ion batteries

Transition metal sulfides have been proved as promising candidates of anode materials for sodium-ion batteries (SIBs) due to their high sodium storage capacity, low cost and enhanced safety. In this study, the amorphous CoS nanoparticle/reduced graphene oxide (CoS/rGO) composite has been fabricated by a facile one-step electron beam radiation route to in situ decorate amorphous CoS nanoparticle on the rGO nanosheets. Benefiting from the small particle size (~2 nm), amorphous structure, and electronic conductive rGO nanosheets, the CoS/rGO nanocomposite exhibits high sodium storage capacity (440 mAh g⁻¹ at 100 mA g⁻¹), excellent cycling stability (277 mAh g⁻¹ after 100 cycles at 200 mA g⁻¹, 79.6% capacity retention) and high rate capability (149.5 mAh g⁻¹ at 2 A g⁻¹). The results provide a facile approach to fabricate promising amorphous and ultrafine metal sulfides for energy storage.     

Synthesis of TiO2(B)/SnO2 composite materials as an anode for lithium-ion batteries

A TiO₂(B) nanosheets/SnO₂ nanoparticles composite was prepared by the hydrothermal and chemical bath deposition (CBD) methods, and its electrochemical properties were investigated for use as the anode material of a lithium-ion battery. The as-prepared composites consisted of monoclinic-phase TiO₂(B) nanosheets and cassiterite structure SnO₂ nanoparticles, in which SnO₂ nanoparticles were uniformly decorated on the TiO₂(B) nanosheets. The TiO₂(B)/SnO₂ composites showed a higher reversible capacity and better durability than that of the pure TiO₂(B) for use as a battery anode. The composite electrodes exhibiting a high initial discharge capacity of 2239.1 mAh g⁻¹ and a discharge capacity of more than 868.7 mAh g⁻¹ could be maintained after 50 cycles at 0.1 C in a voltage range of 1.0–3.0 V at room temperature. The results suggest that TiO₂(B) nanosheets coated with SnO₂ could be suitable for use as a stable anode material for lithium-ion batteries. In addition, the coulombic efficiency of the nanosheets remains at an average of 93.1% for the 3rd–50th cycles.     

Mesoporous N-containing carbon nanosheets towards high-performance electrochemical capacitors

We developed a direct carbonization strategy to efficiently fabricate mesoporous N-containing carbon nanosheets (N-CNSs) by using polyaniline nanosheets as a carbon precursor. Physicochemical characterizations revealed that the as-synthesized N-CNSs with 5.9 wt.% N species possessed a well-developed mesoporous architecture with large specific surface area of 352 m² g⁻¹, high mesoporous volume of 0.32 cm³ g⁻¹, and average pore size of ∼5.2 nm. When further utilized as an electrode for electrochemical capacitors, the mesoporous N-CNSs delivered a large specific capacitance of 239 F g⁻¹ at 0.5 A g⁻¹, and even 197 F g⁻¹ at a high current load of 8 A g⁻¹, indicating its good rate behavior. Furthermore, the capacitance degradation of ∼4% over continuous 5000 charge–discharge cycles at 6 A g⁻¹ further verified its good electrochemical stability at high rates for long-term electrochemical capacitors application.     

Nitrogen-doped carbon nanofibers derived from polyacrylonitrile for use as anode material in sodium-ion batteries

Nitrogen-doped carbon nanofibers (N-CNFs) derived from polyacrylonitrile were successfully synthesized by a combination of electrospinning and thermal treatment processes. The as-prepared N-CNFs were used as anode material for sodium-ion batteries due to their unique fabric and weakly-ordered turbostratic structure as well as large spacing between graphene layers. Results show that N-CNFs carbonized at 800 °C delivered a high reversible capacity of 293 mAh g⁻¹ at a current density of 50 mA g⁻¹ in the first cycle. Even though the first-cycle Coulombic efficiency was 64%, it increased to nearly 100% only after a few initial cycles. Additionally, these N-CNFs showed excellent cycling and high-rate performance, and maintained a capacity of up to 150 mAh g⁻¹ even at an extremely high current density of 1000 mA g⁻¹ for over 200 cycles. It is, therefore, demonstrated that N-CNFs prepared under appropriate conditions are promising anode material candidate for sodium-ion batteries.     

Integration of tailored reduced graphene oxide nanosheets and electrospun polyamide-66 nanofabrics for a flexible supercapacitor with high-volume- and high-area-specific capacitance

Nanofiber fabric is firstly introduced to replace common microfiber fabrics as the platform for flexible supercapacitors. Nanofiber and microfiber electrodes can be simply fabricated using a dipping process that impregnates reduced graphene oxide (RGO) nanosheets into electrospun polyamide-66 (PA66) nanofiber and microfiber fabrics. RGO nanosheets are tailored to various sizes and only RGO with a medium diameter of 250–450 nm (denoted as M-RGO) can effectively penetrate the pores of nanofiber fabrics for constructing smooth conductive paths within PA66 nanofiber fabrics. The synergistic effect between suitable sizes of RGO nanosheets and nanofiber fabrics with a high specific area provides a symmetric supercapacitor composed of M-RGO/PA66 nanofiber fabric electrodes with high-volume and high-area specific capacitance (C_S,V and C_S,A, equal to 38.79 F cm⁻³ and 0.931 F cm⁻² at 0.5 A g⁻¹, respectively), which are much larger than that of a symmetric supercapacitor composed of RGO/PA66 microfiber fabric electrodes (8.52 F cm⁻³ and 0.213 F cm⁻² at 0.5 A g⁻¹). The effect of impregnating nanofiber fabrics with suitably sized RGO to promote C_S,V and C_S,A of flexible supercapacitors has been demonstrated.     

Electrochemical performance of graphitized carbide-derived-carbon with hierarchical micro- and meso-pores in alkaline electrolyte

Graphitized carbide-derived-carbon (CDC) with hierarchical micro- and meso-pores is synthesized by chlorination of titanium carbide powder at 1000 °C. The produced CDC has many bilayer graphenes and some narrow graphite ribbons, which contributes a large amount of micropores (∼1.35 nm) and some mesopores. Although hierarchical pore is an attractive structure for supercapacitor, the low hydrophilicity of the graphitized CDC leads to poor electrochemical performance in alkaline electrolyte. The specific capacitance of the CDC in KOH aqueous electrolyte is only 5 F g⁻¹. A strategy that adding ethanol to alkaline electrolyte is presented to improve its surface wettability. The specific capacitance of the graphitized CDC in KOH aqueous electrolyte with addition of ethanol increases to 60 F g⁻¹ at a scan rate of 20 mV s⁻¹. The optimal content of ethanol in KOH electrolyte is 10 wt.%. In addition, cyclic voltammogram curve can maintain a quasi-rectangular shape well even at a scan rate of 500 mV s⁻¹ and the retention rate of the specific capacitance is about 70%. The specific capacitance is stable at high current density (e.g. 1 A g⁻¹), and almost no performance degradation is observed after 8000 consecutive cycles.     

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.     

Porous nitrogen doped carbon sphere as high performance anode of sodium-ion battery

The carbon material is regarded as the most promising anode candidate for sodium ion battery. In this paper, we found that the porous structure is a critical factor for the improving of carbon anode material. Porous structure is successfully fabricated in nitrogen doped carbon sphere (N-CS) via the mature template-assisted method and the sodium storage property of the porous nitrogen doped carbon sphere (P-N-CS) and N-CS is investigated. The results show that the P-N-CS possesses super rate capability of 155 mAh g⁻¹ at 1 A g⁻¹, which is much higher than that of N-CS (18 mAh g⁻¹). In addition, the P-N-CS exhibits outstanding cycle stability with 206 mAh g⁻¹ after 600 cycles at 0.2 A g⁻¹ and the capacity of N-CS is only 96 mAh g⁻¹ at the same condition. The super electrochemical performance of P-N-CS could be attributed to the high content of pores. Moreover, the high content of pyridinic and graphitic N could facilitate the transfer of sodium ion and electron.     

NiO/C nanocapsules with onion-like carbon shell as anode material for lithium ion batteries

The synthesis of NiO/C nanocapsules with NiO nanoparticles as the core and onion-like carbon layers as the shell is reported. The NiO/C nanocapsules deliver an initial discharge capacity of 1689.4 mAh g⁻¹ at 0.5 C and maintain a high reversible capacity of 1157.7 mAh g⁻¹ after 50 cycles compared to the NiO nanoparticles of 383.5 mAh g⁻¹. As an anode material for lithium ion batteries, the NiO/C nanocapsules exhibit a remarkable discharge capacity, a high rate charge–discharge capability and an excellent cycling stability. The improvements are ascribed to the fact that the onion-like carbon shells not only can provide enough voids to accommodate the volume change of NiO nanoparticles but also can prevent the formation of solid electrolyte interface (SEI) films on the surface of the NiO nanoparticles and hence the direct contact of Ni and SEI films upon lithium extraction.     

Electrochemical cycling behaviour of lithium carbonate (Li2CO3) pre-treated graphite anodes – SEI formation and graphite damage mechanisms

Graphite electrode surfaces were treated using a simple process of sedimentation in aqueous solutions containing 0.5 and 1.0 wt.% Li₂CO₃ with particle sizes of ∼1–2 μm. During the first cycle of voltammetry tests (vs. Li/Li⁺), the graphite surface was subjected to electrochemical degradation as a result of fracture and removal of near-surface graphite particles. Surface degradation was accompanied by a 0.4% strain in the graphite lattice as determined by in situ Raman spectroscopy. Pre-treated electrodes experienced a capacity drop of 3% in the first cycle, compared to a 40% drop observed in case of untreated graphite electrodes. After testing for 100 cycles, a capacity of 0.54 mAh cm⁻² was recorded for the pre-treated electrodes as opposed to a significant drop to 0.11 mAh cm⁻² for the untreated graphite. Cross-sectional HR-TEM indicated that the SEI formed on the pre-treated electrodes primarily consisted of Li₂CO₃ crystals of 14.6 ± 6.9 nm in size distributed within an amorphous matrix. The results suggested that the Li₂CO₃ enriched SEI formed on the pre-treated electrodes reduced the intensity of solvent co-intercalation induced surface damage. It is proposed that the Li₂CO₃ enriched SEI facilitated Li⁺ diffusion and hence improved the capacity retention during long-term cycling.     

Facile synthesis of porous hollow Co3O4 microfibers derived-from metal-organic frameworks as an advanced anode for lithium ion batteries

Co₃O₄, as a promising anode material for the next generation lithium ion batteries to replace graphite, displays high theoretical capacity (890 mAh g⁻¹) and excellent electrochemical properties. However, the drawbacks of its poor cycle performance caused by large volume changes during charge-discharge process and low initial coulombic efficiency due to large irreversible reaction impede its practical application. Herein, we have developed a porous hollow Co₃O₄ microfiber with 500 nm diameter and 60 nm wall thickness synthesized via a facile chemical precipitation method with subsequent thermal decomposition. As an advanced anode for lithium ion batteries, the porous hollow Co₃O₄ microfibers deliver an obviously enhanced electrochemical property in terms of lithium storage capacity (1177.4 mA h g⁻¹ at 100 mA g⁻¹), initial coulombic efficiency (82.9%) and cycle performance (76.6% capacity retention at 200th cycle). This enhancement could be attributed to the well-designed microstructure of porous hollow Co₃O₄ microfibers, which could increase the contact surface area between electrolyte and active materials and accommodate the volume variations via additional void space during cycling.     

Ag enhanced electrochemical performance for Na2Li2Ti6O14 anode in rechargeable lithium-ion batteries

Due to the characteristics of an electronic insulator, Na₂Li₂Ti₆O₁₄ always suffers from low electronic conductivity as anode material for lithium storage. Via Ag coating, Na₂Li₂Ti₆O₁₄@Ag is fabricated, which has higher electronic conductivity than bare Na₂Li₂Ti₆O₁₄. Enhancing the Ag coating content from 0.0 to 10.0 wt%, the surface of Na₂Li₂Ti₆O₁₄ is gradually deposited by Ag nanoparticles. At 6.0 wt%, a continuous Ag conductive layer is formed on Na₂Li₂Ti₆O₁₄. While, particle growth and aggregation take place when the Ag coating content reaches 10.0 wt%. As a result, Na₂Li₂Ti₆O₁₄@6.0 wt% Ag displays better cycle and rate properties than other samples. It can deliver a lithium storage capacity of 131.4 mAh g⁻¹ at 100 mA g⁻¹, 124.9 mAh g⁻¹ at 150 mA g⁻¹, 119.1 mAh g⁻¹ at 200 mA g⁻¹, 115.8 mAh g⁻¹ at 250 mA g⁻¹, 111.9 mAh g⁻¹ at 300 mA g⁻¹ and 109.4 mAh g⁻¹ at 350 mA g⁻¹, respectively.     

Promising graphene/carbon nanotube foam@π-conjugated polymer self-supporting composite cathodes for high-performance rechargeable lithium batteries

Three-dimensional (3D) graphene foam materials are highly favored due to large accessible surface and excellent conductive network, which can be commendably applied as self-supporting electrodes for advanced rechargeable lithium batteries (RLBs). Here, promising graphene nanosheets/acid-treated multi-walled carbon nanotubes (GNS/aMWCNT)-supported 1,5-diaminoanthraquinone (DAA) organic foams [oGCTF(DAA)] are prepared by organic solvent displacement method followed by solvothermal reaction. And then electrochemical polymerization is carried out to obtain 3D porous GNS/aMWCNT organic foam-supported poly(1,5-diaminoanthraquinone) (oGCTF@PDAA) nanocomposites, which achieves the ordered growth of homogeneous PDAA nanoparticles on GNS/aMWCNT surface due to the role of oGCTF(DAA). Such structure largely improves PDAA utilization, facilitates charge transportation and suppresses the dissolution of PDAA. As a result, the oGCTF@PDAA cathode for RLBs delivers a high discharge capacity of 289 mAh g⁻¹ at 30 mA g⁻¹ and still retains 122 mAh g⁻¹ at extreme 10 A g⁻¹ for rapid charging/discharging. Moreover, superior cycling stability is achieved with only 14.8% capacity loss after 2000 cycles even at a high current density of 1 A g⁻¹.     

Functionalized N-doped interconnected carbon nanofibers as an anode material for sodium-ion storage with excellent performance

The electrochemical performance of sodium-ion battery was improved by using functionalized interconnected N-doped carbon nanofibers (FN-CNFs) as the anode. The material was synthesized with polypyrrole as precursor by a simple method. The FN-CNF electrode exhibits excellent rate capability and cycling stability, delivering a capacity of 134.2 mAh g⁻¹ at a high current density of 200 mA g⁻¹ after 200 cycles and retains a capacity of 73 mAh g⁻¹ even at an extremely high current density of 20 A g⁻¹. The superior performance can be attributed to N-doped sites and functionalized groups, which are capable of capturing sodium ions rapidly and reversibly through surface adsorption and surface redox reactions.